Pentagonal-bipyramidal Dysprosium(III) complexes with two apical phosphine oxide ligands and equatorial pentadentate N3O2 Schiff-base ligands: Breakdown of the apical magnetic axiality by strong equatorial crystal field†

IF 6.1 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Inorganic Chemistry Frontiers Pub Date : 2024-11-12 DOI:10.1039/d4qi02262a
Tamara A. Bazhenova, Vyacheslav Kopotkov, Denis V. Korchagin, Elena Yureva, Michael V. Zhidkov, Alexey I Dmitriev, Ilya Yakushev, N. N. Efimov, Konstantin Andreevich Babeshkin, Vladimir Sergeevich Mironov, Eduard B. Yagubskii
{"title":"Pentagonal-bipyramidal Dysprosium(III) complexes with two apical phosphine oxide ligands and equatorial pentadentate N3O2 Schiff-base ligands: Breakdown of the apical magnetic axiality by strong equatorial crystal field†","authors":"Tamara A. Bazhenova, Vyacheslav Kopotkov, Denis V. Korchagin, Elena Yureva, Michael V. Zhidkov, Alexey I Dmitriev, Ilya Yakushev, N. N. Efimov, Konstantin Andreevich Babeshkin, Vladimir Sergeevich Mironov, Eduard B. Yagubskii","doi":"10.1039/d4qi02262a","DOIUrl":null,"url":null,"abstract":"A series of three new seven-coordinate pentagonal-bipyramidal (PBPY-7) Dy(III) complexes [Dy(L<small><sup>CH3</sup></small>)(Cy<small><sub>3</sub></small>PO)<small><sub>2</sub></small>]ClO<small><sub>4</sub></small>∙CH<small><sub>3</sub></small>CN (<strong>1</strong>), [Dy(L<small><sup>2(t-Bu)</sup></small>)(Ph<small><sub>3</sub></small>PO)<small><sub>2</sub></small>]ClO<small><sub>4</sub></small>∙0.63C<small><sub>2</sub></small>H<small><sub>5</sub></small>OH (<strong>2</strong>), [Dy(L<small><sup>OCH3</sup></small>)(Ph<small><sub>3</sub></small>PO)<small><sub>2</sub></small>]ClO<small><sub>4</sub></small>∙2H<small><sub>2</sub></small>O (<strong>3</strong>) including various chelating pentadentate ligands with a [N<small><sub>3</sub></small>O<small><sub>2</sub></small>]<small><sup>2−</sup></small> binding node in the equatorial plane, L<small><sup>CH3</sup></small> = [2,6-diacetylpyridine bis(acetylhydrazone)]<small><sup>2-</sup></small>, L<small><sup>2(t-Bu)</sup></small> = [2,6-diacetylpyridine bis(3,5di-tert-butylbenzoylhydrazone)]<small><sup>2-</sup></small>, L<small><sup>CH3</sup></small> = [2,6-diacetylpyridine bis(4-methoxybenzoylhydrazone)]<small><sup>2-</sup></small>, and two apical Cy<small><sub>3</sub></small>PO and Ph<small><sub>3</sub></small>PO ligands was synthesized and characterized structurally and magnetically. AC magnetic measurements indicated a single-molecule-magnet (SMM) behavior of <strong>1</strong>− <strong>3</strong> with energy barriers of <em>U<small><sub>eff</sub></small></em> ≈ 318−350 K. <em>Ab initio</em> calculations and crystal-field (CF) analysis showed that the ground state of <strong>1</strong>− <strong>3</strong> is a nearly pure Ising type Kramers doublet (KD<small><sub>0</sub></small>) |±15/2&gt; <small><sub>eq</sub></small> with the long magnetic axis lying in the equatorial plane N<small><sub>3</sub></small>O<small><sub>2</sub></small>, as opposite to high-performance PBPY-7 Dy(III) SMMs (<em>U<small><sub>eff</sub></small></em> &gt; 1000 K), where long magnetic axis of KD<small><sub>0</sub></small> |±15/2&gt; invariably points toward apical ligands. This difference is due to competition between the apical and equatorial CFs, which has been quantitatevely examined with CF calculations. We show that the turning of the long magnetic axis (<em>g<small><sub>z</sub></small></em> ~ 19.6) from apical ligands (<em>z</em>) to the equatorial plane (<em>xy</em>) is due to crossover between the oblate |±15/2&gt; and prolate |±1/2&gt; ground states of Dy(III) ion, that occurs at the negative ratio <em>B<small><sub>20</sub></small>/B<small><sub>40</sub></small></em> &lt; –0.07 of two axial CF parameters <em>B<small><sub>20</sub></small></em> and <em>B<small><sub>40</sub></small></em>. Complexes <strong>1</strong>−<strong>3</strong> refer to this case due to strong equatorial CF of the negatively charged chelate node [N<small><sub>3</sub></small>O<small><sub>2</sub></small>]<small><sup>2–</sup></small>producing large positive CF parameter <em>B<small><sub>40</sub></small></em> and negative <em>B<small><sub>20</sub></small></em>. In this case, SMM properties of <strong>1</strong>− <strong>3</strong> arise from distortions of the PBPY-7 complex (namely, from a large O1-Dy-O2 bond angle of ~ 100<small><sup>o</sup></small> in the N<small><sub>3</sub></small>O<small><sub>2</sub></small> pentagon of <strong>1</strong>−<strong>3</strong>) that mix the lowest state |±1/2&gt; and low-lying low-<em>m<small><sub>J</sub></small></em> states to produce the equatorial KD<small><sub>0</sub></small> |±15/2&gt;<small><sub>eq</sub></small>. This highlights a breakdown of the apical magnetic axiality, since the SMM performance of <strong>1</strong>− <strong>3</strong> is governed by a strong equatorial CF and distortions rather than by high <em>D<small><sub>5h</sub></small></em> symmetry and strong apical ligands. Some ways to improve the SMM efficiency of <strong>1</strong>−<strong> 3</strong> and related PBPY-7 Dy(III) complexes are discussed.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":6.1000,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry Frontiers","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4qi02262a","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
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Abstract

A series of three new seven-coordinate pentagonal-bipyramidal (PBPY-7) Dy(III) complexes [Dy(LCH3)(Cy3PO)2]ClO4∙CH3CN (1), [Dy(L2(t-Bu))(Ph3PO)2]ClO4∙0.63C2H5OH (2), [Dy(LOCH3)(Ph3PO)2]ClO4∙2H2O (3) including various chelating pentadentate ligands with a [N3O2]2− binding node in the equatorial plane, LCH3 = [2,6-diacetylpyridine bis(acetylhydrazone)]2-, L2(t-Bu) = [2,6-diacetylpyridine bis(3,5di-tert-butylbenzoylhydrazone)]2-, LCH3 = [2,6-diacetylpyridine bis(4-methoxybenzoylhydrazone)]2-, and two apical Cy3PO and Ph3PO ligands was synthesized and characterized structurally and magnetically. AC magnetic measurements indicated a single-molecule-magnet (SMM) behavior of 13 with energy barriers of Ueff ≈ 318−350 K. Ab initio calculations and crystal-field (CF) analysis showed that the ground state of 13 is a nearly pure Ising type Kramers doublet (KD0) |±15/2> eq with the long magnetic axis lying in the equatorial plane N3O2, as opposite to high-performance PBPY-7 Dy(III) SMMs (Ueff > 1000 K), where long magnetic axis of KD0 |±15/2> invariably points toward apical ligands. This difference is due to competition between the apical and equatorial CFs, which has been quantitatevely examined with CF calculations. We show that the turning of the long magnetic axis (gz ~ 19.6) from apical ligands (z) to the equatorial plane (xy) is due to crossover between the oblate |±15/2> and prolate |±1/2> ground states of Dy(III) ion, that occurs at the negative ratio B20/B40 < –0.07 of two axial CF parameters B20 and B40. Complexes 13 refer to this case due to strong equatorial CF of the negatively charged chelate node [N3O2]2–producing large positive CF parameter B40 and negative B20. In this case, SMM properties of 13 arise from distortions of the PBPY-7 complex (namely, from a large O1-Dy-O2 bond angle of ~ 100o in the N3O2 pentagon of 13) that mix the lowest state |±1/2> and low-lying low-mJ states to produce the equatorial KD0 |±15/2>eq. This highlights a breakdown of the apical magnetic axiality, since the SMM performance of 13 is governed by a strong equatorial CF and distortions rather than by high D5h symmetry and strong apical ligands. Some ways to improve the SMM efficiency of 1 3 and related PBPY-7 Dy(III) complexes are discussed.
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具有两个顶端氧化膦配体和赤道正五态 N3O2 席夫碱配体的五角双金字塔镝(III)配合物:强赤道晶体场打破顶端磁轴性
一系列新的七配位五角双金字塔(PBPY-7)Dy(III)配合物[Dy(LCH3)(Cy3PO)2]ClO4∙CH3CN (1)、[Dy(L2(t-Bu))(Ph3PO)2]ClO4∙0.63C2H5OH (2)、[Dy(LOCH3)(Ph3PO)2]ClO4∙2H2O (3),包括各种螯合五价配体,其赤道面上有一个[N3O2]2-结合节点,LCH3 = [2,6-二乙酰基吡啶双乙酰腙]2-,L2(t-Bu) = [2、LCH3=[2,6-二乙酰基吡啶双(乙酰腙)]2-、L2(t-Bu) = [2,6-二乙酰基吡啶双(3,5-二叔丁基苯甲酰基腙)]2-,以及两个顶端 Cy3PO 和 Ph3PO 配体。交流磁性测量结果表明,1- 3 具有单分子磁(SMM)行为,能量势垒 Ueff ≈ 318-350 K。Ab initio 计算和晶体场(CF)分析表明,1- 3 的基态是一种近乎纯粹的伊辛型克拉默双特(KD0)±15/2> eq,其长磁轴位于 N3O2 的赤道面,这与高性能 PBPY-7 Dy(III) SMM(Ueff > 1000 K)相反,后者的 KD0 长磁轴总是指向顶端配体。这种差异是由于顶端和赤道 CF 之间的竞争造成的,这一点已通过 CF 计算进行了定量研究。我们的研究表明,长磁轴(gz ~ 19.6)从顶端配体(z)转向赤道平面(xy)是由于 Dy(III)离子的扁球形基态(±15/2>)和长球形基态(±1/2>)之间的交叉,发生在两个轴向 CF 参数 B20 和 B40 的负比 B20/B40 < -0.07。由于带负电荷的螯合节点 [N3O2]2 的强赤道 CF 产生了较大的正 CF 参数 B40 和负 B20,因此配合物 1-3 属于这种情况。在这种情况下,1- 3 的 SMM 特性源于 PBPY-7 复合物的扭曲(即 1-3 中 N3O2 五边形中约 100o 的大 O1-Dy-O2 键角),这种扭曲混合了最低态 |±1/2> 和低洼的低-mJ 态,从而产生了赤道 KD0 |±15/2>eq.这凸显了顶端磁轴性的破坏,因为 1- 3 的 SMM 性能是由强赤道 CF 和扭曲而不是由高 D5h 对称性和强顶端配位体决定的。本文讨论了提高 1- 3 和相关 PBPY-7 镝(III)配合物的 SMM 效率的一些方法。
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来源期刊
Inorganic Chemistry Frontiers
Inorganic Chemistry Frontiers CHEMISTRY, INORGANIC & NUCLEAR-
CiteScore
10.40
自引率
7.10%
发文量
587
审稿时长
1.2 months
期刊介绍: The international, high quality journal for interdisciplinary research between inorganic chemistry and related subjects
期刊最新文献
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