Pub Date : 2019-03-04DOI: 10.1080/02603594.2019.1587612
L. E. VanGelder, Timothy R. Cook, E. Matson
ABSTRACT Innovation in the development of electrochemical energy storage methods is essential if these technologies are to meet the variable needs of the electrical grid. Nonaqueous redox flow batteries represent an underdeveloped area of research in energy storage—one which has seen a recent spike in interest owing to the potential for modular, energy-dense electrochemical energy conversion. Here, we summarize our recent work, focused on the design of polyoxovanadate-alkoxide clusters [V6O7(OR)12] as a new class of charge carrier for nonaqueous energy storage. The synthetic strategies we have employed, including homoleptic ligand substitution, selective ligand functionalization, and heterometal installation, demonstrate the flexibility of this hexametalate platform, and result in significant improvement of molecular properties with relevance to flow battery energy density. The identified homoleptic surface modifications (substituting R = CH3 for R = C2H5) to the polyoxovanadate-alkoxide scaffold yield an increase in stable operating voltage window (from 0.6 V to 1.8 V), as well as an increase in the stoichiometric number of electrons that can be stored at each battery electrode (from 1 to 2). Targeted functionalization at the cluster surface with an ether-based ligand affords [V6O7(OC2H5)9(OCH2)3CCH2OC2H4OCH3], which demonstrates a 12-fold increase in solubility over its homoleptic congener, from 0.05 to 0.60 M in acetonitrile. The substitution of a titanium center into the hexametalate core to generate [V5TiO6(OCH3)13]− further increases the voltage window to 2.3 V, as new heterometal-based redox events are introduced to the profile. Through these studies, we have gained valuable insights into the molecular parameters that determine the energy storage capabilities of multimetallic charge carriers. Collectively, our results highlight new opportunities for polynuclear charge carriers, and emphasize the critical role that synthetic inorganic chemistry plays in the development of effective nonaqueous redox flow battery technologies. TOC GRAPHICAL ABSTRACT
{"title":"Progress in the Design of Polyoxovanadate-Alkoxides as Charge Carriers for Nonaqueous Redox Flow Batteries","authors":"L. E. VanGelder, Timothy R. Cook, E. Matson","doi":"10.1080/02603594.2019.1587612","DOIUrl":"https://doi.org/10.1080/02603594.2019.1587612","url":null,"abstract":"ABSTRACT Innovation in the development of electrochemical energy storage methods is essential if these technologies are to meet the variable needs of the electrical grid. Nonaqueous redox flow batteries represent an underdeveloped area of research in energy storage—one which has seen a recent spike in interest owing to the potential for modular, energy-dense electrochemical energy conversion. Here, we summarize our recent work, focused on the design of polyoxovanadate-alkoxide clusters [V6O7(OR)12] as a new class of charge carrier for nonaqueous energy storage. The synthetic strategies we have employed, including homoleptic ligand substitution, selective ligand functionalization, and heterometal installation, demonstrate the flexibility of this hexametalate platform, and result in significant improvement of molecular properties with relevance to flow battery energy density. The identified homoleptic surface modifications (substituting R = CH3 for R = C2H5) to the polyoxovanadate-alkoxide scaffold yield an increase in stable operating voltage window (from 0.6 V to 1.8 V), as well as an increase in the stoichiometric number of electrons that can be stored at each battery electrode (from 1 to 2). Targeted functionalization at the cluster surface with an ether-based ligand affords [V6O7(OC2H5)9(OCH2)3CCH2OC2H4OCH3], which demonstrates a 12-fold increase in solubility over its homoleptic congener, from 0.05 to 0.60 M in acetonitrile. The substitution of a titanium center into the hexametalate core to generate [V5TiO6(OCH3)13]− further increases the voltage window to 2.3 V, as new heterometal-based redox events are introduced to the profile. Through these studies, we have gained valuable insights into the molecular parameters that determine the energy storage capabilities of multimetallic charge carriers. Collectively, our results highlight new opportunities for polynuclear charge carriers, and emphasize the critical role that synthetic inorganic chemistry plays in the development of effective nonaqueous redox flow battery technologies. TOC GRAPHICAL ABSTRACT","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"39 1","pages":"51 - 89"},"PeriodicalIF":5.4,"publicationDate":"2019-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"72869082","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2019-03-04DOI: 10.1080/02603594.2019.1592751
Tarun F. Parangi, M. Mishra
The notable progress in the field of nano-science and nano-technology addresses many environmental and energy applications. Among these, photocatalysis applications have received remarkable attention, where the TiO2 photocatalyst has great potential to play a role in the field of photocatalysis for fuel production and environmental remediation. The present review article deals with the considerable progress in the modification and development of TiO2 nanoparticles (NPs) to improve visible light photocatalytic activity. Graphical abstract
{"title":"Titania Nanoparticles as Modified Photocatalysts: A Review on Design and Development","authors":"Tarun F. Parangi, M. Mishra","doi":"10.1080/02603594.2019.1592751","DOIUrl":"https://doi.org/10.1080/02603594.2019.1592751","url":null,"abstract":"The notable progress in the field of nano-science and nano-technology addresses many environmental and energy applications. Among these, photocatalysis applications have received remarkable attention, where the TiO2 photocatalyst has great potential to play a role in the field of photocatalysis for fuel production and environmental remediation. The present review article deals with the considerable progress in the modification and development of TiO2 nanoparticles (NPs) to improve visible light photocatalytic activity. Graphical abstract","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"17 1","pages":"126 - 90"},"PeriodicalIF":5.4,"publicationDate":"2019-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88373350","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2019-01-02DOI: 10.1080/02603594.2018.1559158
Waleed Yaseen, S. Sanders, Ruaa M. Almotawa, Brooke M. Otten, Sonali Bhat, Domllermut Alamo, S. Marpu, T. Golden, M. Omary
This article provides a second manifestation of a new tradition by which the editors of Comments on Inorganic Chemistry wish to lead by example, whereby we start publishing original research content that, nonetheless, preserves the Journal’s identity as a niche for “critical discussion of the current literature” of inorganic chemistry. (For the first manifestation, see: Otten, B. M.; Melancon, K. M.; Omary, M. A. “All That Glitters is Not Gold: A Computational Study of Covalent vs Metallophilic Bonding in Bimetallic Complexes of d10 Metal Centers—A Tribute to Al Cotton on the 10th Anniversary of His Passing,” Comments Inorg. Chem. 2018, 38, 1–35.) Thus, herein we show that a trinuclear copper (I) complex {[3,5-(CF3)2Pz]Cu}3 (henceforth referred to as the “Cu trimer”) can act as a “metal-organic coating” for corrosion protection of aluminum, whereas its silver analogue, {[3,5-(CF3)2Pz]Ag}3 (i.e., the “Ag trimer”), could not. The manuscript was initially submitted to journals that usually publish on “organic coatings” but was rejected on the premise that a metal complex cannot be considered “organic” unless it is incorporated into a polymer. This issue is commented upon herein in the broader context of whether to consider metal complexes “organic,” “inorganic,” “organometallic,” or “metal-organic” materials with manifestations of the use of each classification in the literature. We have found that, upon coating the Cu trimer onto an aluminum (AA 3003) surface, potentiodynamic polarization results in 3.5% NaCl show an increase in corrosion potential (Ecorr) by ~ 0.6 V concomitant with a three-order-of-magnitude decrease in corrosion current density (icorr) from 0.025 µA/cm2 for uncoated aluminum to ~ 9.6 × 10–5 µA/cm2 for the Cu trimer-coated surface. With a double coating, the Cu trimer formed a completely insulating surface with no current flow, even at very high potential magnitude and range. Open circuit potential was used to study the stability of the Cu trimer films on the Al surface in the electrolyte solution. Scanning electron microscopy and Fourier-transform infrared spectroscopy techniques were used to characterize the structure of both the Cu trimer powder and Cu trimer film on the aluminum surface before and after the corrosion tests. The hydrophobicity of the Cu trimer coating was determined by using water drop contact angle measurements, which demonstrated an increase from 65° to 137° for the uncoated and coated aluminum, respectively. The thermal stability of the Cu trimer was analyzed using thermogravimetric analysis, giving rise to weight loss resistance up to ~190 °C. The results clearly demonstrate that the Cu trimer layers exhibit superior stability and potential for corrosion protection of aluminum surfaces in corrosive environments. The Ag trimer analogue, meanwhile, failed the “tape test” that the Cu trimer passed to assess the mechanical stability of such “metal-organic” coatings. Density functional theory (DFT) simulations
这篇文章提供了《无机化学评论》编辑们希望以史为鉴的新传统的第二种表现，即我们开始发表原创研究内容，尽管如此，保留了该杂志作为无机化学“当前文献批判性讨论”的利基的身份。(关于第一种表现，请参见:Otten, b.m.;梅兰康，k.m.;“所有闪光的都不是黄金:d10金属中心双金属配合物中共价与亲金键的计算研究——纪念Al Cotton逝世10周年”，Inorg评论。化学，2018,38,1-35。因此，本文表明，三核铜(I)配合物{[3,5-(CF3)2Pz]Cu}3(以下称为“Cu三聚体”)可以作为“金属有机涂层”保护铝，而其银类似物{[3,5-(CF3)2Pz]Ag}3(即“Ag三聚体”)则不能。该手稿最初被提交给通常发表“有机涂层”的期刊，但被拒绝，因为前提是金属配合物不能被认为是“有机的”，除非它被纳入聚合物中。这个问题是在更广泛的背景下进行评论的，即是否将金属配合物视为“有机”、“无机”、“有机金属”或“金属-有机”材料，并在文献中使用每种分类的表现。我们发现，在铝(AA 3003)表面涂覆Cu三聚体后，3.5% NaCl的动电位极化结果表明，腐蚀电位(Ecorr)增加了0.6 V，腐蚀电流密度(icorr)从未涂覆铝的0.025 μ a /cm2下降到涂覆Cu三聚体表面的9.6 × 10-5 μ a /cm2。通过双重涂层，铜三聚体形成了一个完全绝缘的表面，即使在非常高的电位幅度和范围下也没有电流流过。利用开路电位研究了铝表面Cu三聚体膜在电解质溶液中的稳定性。采用扫描电镜和傅里叶变换红外光谱技术对腐蚀试验前后铝表面Cu三聚体粉末和Cu三聚体膜的结构进行了表征。用水滴接触角测定了Cu三聚体涂层的疏水性，结果表明，未涂覆和涂覆的铝的疏水性分别从65°增加到137°。用热重法分析了Cu三聚体的热稳定性，结果表明Cu三聚体在~190℃下具有良好的耐失重性能。结果清楚地表明，Cu三聚体层在腐蚀环境中表现出优异的稳定性和对铝表面的腐蚀保护潜力。与此同时，银三聚体类似物未能通过铜三聚体通过的“胶带测试”，以评估这种“金属有机”涂层的机械稳定性。密度泛函理论(DFT)模拟一方面通过模拟每个环三聚体分子(和其他类似分子)与Al原子的相互作用，并将所得到的结合能与每个三聚体的金相结合的晶体固体形式的相应解离能进行对比，从而提供了对这种差异的见解。因此，发现Ag三聚体模型与Al原子的结合至少与Cu三聚体模型一样强;然而，这种成键还不够高，不足以克服亲银吸引，而它可以克服亲铜吸引。对于三聚体与氧化铝的相互作用以及铜三聚体的部分氧化也给出了其他解释，这加强了与Al原子的相互作用。图形抽象
{"title":"Are Metal Complexes “Organic,” “Inorganic,” “Organometallic,” or “Metal-Organic” Materials? A case Study for the Use of Trinuclear Coinage Metal Complexes as “Metal-Organic Coatings” for Corrosion Suppression on Aluminum Substrates","authors":"Waleed Yaseen, S. Sanders, Ruaa M. Almotawa, Brooke M. Otten, Sonali Bhat, Domllermut Alamo, S. Marpu, T. Golden, M. Omary","doi":"10.1080/02603594.2018.1559158","DOIUrl":"https://doi.org/10.1080/02603594.2018.1559158","url":null,"abstract":"This article provides a second manifestation of a new tradition by which the editors of Comments on Inorganic Chemistry wish to lead by example, whereby we start publishing original research content that, nonetheless, preserves the Journal’s identity as a niche for “critical discussion of the current literature” of inorganic chemistry. (For the first manifestation, see: Otten, B. M.; Melancon, K. M.; Omary, M. A. “All That Glitters is Not Gold: A Computational Study of Covalent vs Metallophilic Bonding in Bimetallic Complexes of d10 Metal Centers—A Tribute to Al Cotton on the 10th Anniversary of His Passing,” Comments Inorg. Chem. 2018, 38, 1–35.) Thus, herein we show that a trinuclear copper (I) complex {[3,5-(CF3)2Pz]Cu}3 (henceforth referred to as the “Cu trimer”) can act as a “metal-organic coating” for corrosion protection of aluminum, whereas its silver analogue, {[3,5-(CF3)2Pz]Ag}3 (i.e., the “Ag trimer”), could not. The manuscript was initially submitted to journals that usually publish on “organic coatings” but was rejected on the premise that a metal complex cannot be considered “organic” unless it is incorporated into a polymer. This issue is commented upon herein in the broader context of whether to consider metal complexes “organic,” “inorganic,” “organometallic,” or “metal-organic” materials with manifestations of the use of each classification in the literature. We have found that, upon coating the Cu trimer onto an aluminum (AA 3003) surface, potentiodynamic polarization results in 3.5% NaCl show an increase in corrosion potential (Ecorr) by ~ 0.6 V concomitant with a three-order-of-magnitude decrease in corrosion current density (icorr) from 0.025 µA/cm2 for uncoated aluminum to ~ 9.6 × 10–5 µA/cm2 for the Cu trimer-coated surface. With a double coating, the Cu trimer formed a completely insulating surface with no current flow, even at very high potential magnitude and range. Open circuit potential was used to study the stability of the Cu trimer films on the Al surface in the electrolyte solution. Scanning electron microscopy and Fourier-transform infrared spectroscopy techniques were used to characterize the structure of both the Cu trimer powder and Cu trimer film on the aluminum surface before and after the corrosion tests. The hydrophobicity of the Cu trimer coating was determined by using water drop contact angle measurements, which demonstrated an increase from 65° to 137° for the uncoated and coated aluminum, respectively. The thermal stability of the Cu trimer was analyzed using thermogravimetric analysis, giving rise to weight loss resistance up to ~190 °C. The results clearly demonstrate that the Cu trimer layers exhibit superior stability and potential for corrosion protection of aluminum surfaces in corrosive environments. The Ag trimer analogue, meanwhile, failed the “tape test” that the Cu trimer passed to assess the mechanical stability of such “metal-organic” coatings. Density functional theory (DFT) simulations ","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"22 1","pages":"1 - 26"},"PeriodicalIF":5.4,"publicationDate":"2019-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73391737","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2019-01-02DOI: 10.1080/02603594.2019.1570165
Zhong-Jian Cai, Dawei Xiao, L. Do
In this tutorial, we describe the applications of well-defined heterobimetallic complexes in coordination insertion polymerization catalysis. The presence of two different metals in a single catalyst platform imparts reactivity patterns that are distinct from those of their homobimetallic and monometallic counterparts. We will demonstrate that heterobimetallic complexes are a versatile and unique class of catalysts by providing representative examples from recent studies of carbon dioxide/epoxide, lactone, lactide, and olefin polymerization. We will focus on the various strategies employed to synthesize mixed metal species, methods to characterize their structures, and the mechanistic roles of the metal ions during polymerization. Graphical Abstract
{"title":"Cooperative Heterobimetallic Catalysts in Coordination Insertion Polymerization","authors":"Zhong-Jian Cai, Dawei Xiao, L. Do","doi":"10.1080/02603594.2019.1570165","DOIUrl":"https://doi.org/10.1080/02603594.2019.1570165","url":null,"abstract":"In this tutorial, we describe the applications of well-defined heterobimetallic complexes in coordination insertion polymerization catalysis. The presence of two different metals in a single catalyst platform imparts reactivity patterns that are distinct from those of their homobimetallic and monometallic counterparts. We will demonstrate that heterobimetallic complexes are a versatile and unique class of catalysts by providing representative examples from recent studies of carbon dioxide/epoxide, lactone, lactide, and olefin polymerization. We will focus on the various strategies employed to synthesize mixed metal species, methods to characterize their structures, and the mechanistic roles of the metal ions during polymerization. Graphical Abstract","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"1 1","pages":"27 - 50"},"PeriodicalIF":5.4,"publicationDate":"2019-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89073618","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-11-02DOI: 10.1080/02603594.2018.1539392
Lei Liu, Wes Lee, Mingbin Yuan, O. Gutierrez
In this comment, we present recent insights into the mechanism of bisphosphine-iron catalyzed C(sp2)-C(sp3) cross-coupling reactions (CCRs) with the focus on the nature of the C-C bond formation event (inner-sphere versus outer-sphere) as revealed by quantum mechanical calculations from our group and others. Implications for reaction and catalyst design principles are discussed. Graphical Abstract
{"title":"Mechanisms of Bisphosphine Iron-Catalyzed C(SP2)-C(SP3) Cross-Coupling Reactions: Inner-Sphere or Outer-Sphere Arylation?","authors":"Lei Liu, Wes Lee, Mingbin Yuan, O. Gutierrez","doi":"10.1080/02603594.2018.1539392","DOIUrl":"https://doi.org/10.1080/02603594.2018.1539392","url":null,"abstract":"In this comment, we present recent insights into the mechanism of bisphosphine-iron catalyzed C(sp2)-C(sp3) cross-coupling reactions (CCRs) with the focus on the nature of the C-C bond formation event (inner-sphere versus outer-sphere) as revealed by quantum mechanical calculations from our group and others. Implications for reaction and catalyst design principles are discussed. Graphical Abstract","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"195 1","pages":"210 - 237"},"PeriodicalIF":5.4,"publicationDate":"2018-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75885136","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-11-02DOI: 10.1080/02603594.2018.1542597
Yoshie Sakamaki, John Ozdemir, Zachary Heidrick, O. Watson, Hamid R. Shahsavari, Masood Fereidoonnezhad, A. Khosropour, Hassan Beyzavi
We describe the newest approach to photodynamic therapy (PDT) using metal-organic frameworks (MOFs) and covalent organic frameworks (COFs). PDT’s characteristic method of treating cancer as noninvasive and selective has garnered much attention. PDT has entered the realm of nanotechnology to overcome various challenges that are hindering its effectiveness. Porous materials, which are more functional than small molecules, are being explored as platforms for PDT. MOFs are at the forefront of these investigations, and the anti-tumor ability of well-designed nano-MOFs (nMOFs) has recently been reported. We also discuss the possibility of using COFs for future-use PDT.
{"title":"Metal–Organic Frameworks and Covalent Organic Frameworks as Platforms for Photodynamic Therapy","authors":"Yoshie Sakamaki, John Ozdemir, Zachary Heidrick, O. Watson, Hamid R. Shahsavari, Masood Fereidoonnezhad, A. Khosropour, Hassan Beyzavi","doi":"10.1080/02603594.2018.1542597","DOIUrl":"https://doi.org/10.1080/02603594.2018.1542597","url":null,"abstract":"We describe the newest approach to photodynamic therapy (PDT) using metal-organic frameworks (MOFs) and covalent organic frameworks (COFs). PDT’s characteristic method of treating cancer as noninvasive and selective has garnered much attention. PDT has entered the realm of nanotechnology to overcome various challenges that are hindering its effectiveness. Porous materials, which are more functional than small molecules, are being explored as platforms for PDT. MOFs are at the forefront of these investigations, and the anti-tumor ability of well-designed nano-MOFs (nMOFs) has recently been reported. We also discuss the possibility of using COFs for future-use PDT.","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"4 1","pages":"238 - 293"},"PeriodicalIF":5.4,"publicationDate":"2018-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90567167","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-09-03DOI: 10.1080/02603594.2018.1545225
Xinlin Li, Karan Maindan, P. Deria
Metal-organic frameworks (MOFs) are porous molecular compositions quickly emerging as a novel electro-optical platform, especially for various energy transduction processes. Such functionalities are intimately tied with the modular MOF chemistry required for the delineation of the wide range of tunable porous structures constructed from various electrooptically active linkers and or metal nodes. Various post-synthesis approaches further facilitate incorporation of key chemical functionalities that cannot be introduced into MOFs directly via de novo syntheses. While the tunable frameworks can provide a high areal concentration of electrooptically active species, the pore channels ensure substrate and ion flux, making these compositions highly accessible solid arrangements of molecular catalysts ideal for electro- and photoelectro chemical transformations. The recent surge of literature reports suggests unique features of energy and electron transfer processes within these framework compositions. Thus, understanding the unique features of electron transfer processes within the frameworks will help to delineate strategies for future functional materials. This review highlights some exemplary MOFs’ electrocatalysis to understand the interplay between catalytic and ET processes.
{"title":"Metal-Organic Frameworks-Based Electrocatalysis: Insight and Future Perspectives","authors":"Xinlin Li, Karan Maindan, P. Deria","doi":"10.1080/02603594.2018.1545225","DOIUrl":"https://doi.org/10.1080/02603594.2018.1545225","url":null,"abstract":"Metal-organic frameworks (MOFs) are porous molecular compositions quickly emerging as a novel electro-optical platform, especially for various energy transduction processes. Such functionalities are intimately tied with the modular MOF chemistry required for the delineation of the wide range of tunable porous structures constructed from various electrooptically active linkers and or metal nodes. Various post-synthesis approaches further facilitate incorporation of key chemical functionalities that cannot be introduced into MOFs directly via de novo syntheses. While the tunable frameworks can provide a high areal concentration of electrooptically active species, the pore channels ensure substrate and ion flux, making these compositions highly accessible solid arrangements of molecular catalysts ideal for electro- and photoelectro chemical transformations. The recent surge of literature reports suggests unique features of energy and electron transfer processes within these framework compositions. Thus, understanding the unique features of electron transfer processes within the frameworks will help to delineate strategies for future functional materials. This review highlights some exemplary MOFs’ electrocatalysis to understand the interplay between catalytic and ET processes.","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"57 1","pages":"166 - 209"},"PeriodicalIF":5.4,"publicationDate":"2018-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77745771","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-07-04DOI: 10.1080/02603594.2018.1509856
Wei‐chen Chang, Pinghua Liu, Yisong Guo
Iron(II)- and α-ketoglutarate-dependent (Fe/αKG) enzymes catalyze a large array of reactions. Although hydroxylation reaction catalyzed by these enzymes has been investigated in great details, involving the ferryl (FeIV=O) as a key reactive intermediate. The mechanisms of reactions other than hydroxylation are still largely unknown. By using a combined biochemical, bio-organic, and spectroscopic approach, we have studied the mechanisms of two newly discovered Fe/αKG enzymes, FtmOx1 (endoperoxidase) and AsqJ (desaturase/epoxidase), revealing their strategies in controlling reactivity, namely the effect of redox/polar residues near the iron center, the electronic properties of the substrate, and the intrinsic reactivity of the ferryl intermediate.
{"title":"Mechanistic Elucidation of Two Catalytically Versatile Iron(II)- and α-Ketoglutarate-Dependent Enzymes: Cases Beyond Hydroxylation","authors":"Wei‐chen Chang, Pinghua Liu, Yisong Guo","doi":"10.1080/02603594.2018.1509856","DOIUrl":"https://doi.org/10.1080/02603594.2018.1509856","url":null,"abstract":"Iron(II)- and α-ketoglutarate-dependent (Fe/αKG) enzymes catalyze a large array of reactions. Although hydroxylation reaction catalyzed by these enzymes has been investigated in great details, involving the ferryl (FeIV=O) as a key reactive intermediate. The mechanisms of reactions other than hydroxylation are still largely unknown. By using a combined biochemical, bio-organic, and spectroscopic approach, we have studied the mechanisms of two newly discovered Fe/αKG enzymes, FtmOx1 (endoperoxidase) and AsqJ (desaturase/epoxidase), revealing their strategies in controlling reactivity, namely the effect of redox/polar residues near the iron center, the electronic properties of the substrate, and the intrinsic reactivity of the ferryl intermediate.","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"17 1","pages":"127 - 165"},"PeriodicalIF":5.4,"publicationDate":"2018-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87610576","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-05-04DOI: 10.1080/02603594.2018.1486303
S. Cotton
X-ray diffraction studies on scandium salts in solution and in the solid state, have afforded Sc-O bond lengths in the ions [Sc(H2O)n]3+ (n = 6, 7 and 8) as well as for several compounds containing [(H2O)5Sc(μ-OH)2Sc(H2O)5]4+ ions. Several theoretical studies have examined different models for the aqua ion without finding agreement. This review considers these studies. Diffraction results from solutions yield bond lengths which are compared with species of known geometry and coordination number in the solid state, and with different quantum mechanical predictions. On balance, it is considered that a seven-coordinate [Sc(OH2)7]3+ ion is the species found in solution. GRAPHICAL ABSTRACT
{"title":"The Scandium Aqua Ion Revisited","authors":"S. Cotton","doi":"10.1080/02603594.2018.1486303","DOIUrl":"https://doi.org/10.1080/02603594.2018.1486303","url":null,"abstract":"X-ray diffraction studies on scandium salts in solution and in the solid state, have afforded Sc-O bond lengths in the ions [Sc(H2O)n]3+ (n = 6, 7 and 8) as well as for several compounds containing [(H2O)5Sc(μ-OH)2Sc(H2O)5]4+ ions. Several theoretical studies have examined different models for the aqua ion without finding agreement. This review considers these studies. Diffraction results from solutions yield bond lengths which are compared with species of known geometry and coordination number in the solid state, and with different quantum mechanical predictions. On balance, it is considered that a seven-coordinate [Sc(OH2)7]3+ ion is the species found in solution. GRAPHICAL ABSTRACT","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"96 1","pages":"110 - 125"},"PeriodicalIF":5.4,"publicationDate":"2018-05-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77089639","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-05-04DOI: 10.1080/02603594.2018.1465939
Bennett J. Eleazer, D. V. Peryshkov
Metalated three-dimensional icosahedral boron clusters often exhibit high chemical and thermal stability relative to their simple borane counterparts thus making them a convenient object to study the chemistry of metal-boron bonds. The presence of multiple reactive boron vertices makes carboranes unique ligands with unusual steric and electronic requirements. This article summarizes recent developments in coordination chemistry of neutral {C2B10} carborane clusters with a focus on metal-boron interactions. Several bonding modes are discussed, including neutral borane coordination through bridging B–H··· M interactions, boryl complexes with B -M bonds, multimetallic assemblies, and the BB-carboryne complex containing a three-membered (BB)>Ru metallacycle.
{"title":"Coordination Chemistry of Carborane Clusters: Metal-Boron Bonds in Carborane, Carboranyl, and Carboryne Complexes","authors":"Bennett J. Eleazer, D. V. Peryshkov","doi":"10.1080/02603594.2018.1465939","DOIUrl":"https://doi.org/10.1080/02603594.2018.1465939","url":null,"abstract":"Metalated three-dimensional icosahedral boron clusters often exhibit high chemical and thermal stability relative to their simple borane counterparts thus making them a convenient object to study the chemistry of metal-boron bonds. The presence of multiple reactive boron vertices makes carboranes unique ligands with unusual steric and electronic requirements. This article summarizes recent developments in coordination chemistry of neutral {C2B10} carborane clusters with a focus on metal-boron interactions. Several bonding modes are discussed, including neutral borane coordination through bridging B–H··· M interactions, boryl complexes with B -M bonds, multimetallic assemblies, and the BB-carboryne complex containing a three-membered (BB)>Ru metallacycle.","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"63 1","pages":"109 - 79"},"PeriodicalIF":5.4,"publicationDate":"2018-05-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90884664","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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