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源自氧化还原活性赤道四硫富瓦烯席夫碱配体的二价铁自旋交叉配位聚合物。

Iron(II) Spin Crossover Coordination Polymers Derived From a Redox Active Equatorial Tetrathiafulvalene Schiff-Base Ligand.

作者信息

Qiu Ya-Ru, Cui Long, Ge Jing-Yuan, Kurmoo Mohamedally, Ma Guijun, Su Jian

机构信息

School of Physical Science and Technology, ShanghaiTech University, Shanghai, China.

State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing, China.

出版信息

Front Chem. 2021 Aug 2;9:692939. doi: 10.3389/fchem.2021.692939. eCollection 2021.

DOI:10.3389/fchem.2021.692939
PMID:34409015
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8365465/
Abstract

Two polymorphic Fe coordination polymers [FeL (TPPE)] ) and [(Fe L (TPPE))] ), were obtained from a redox-active tetrathiafulvalene (TTF) functionalized ligand [HL = 2,2'-(((2-(4,5-bis-(methylthio)-1,3-dithiol-2-ylidene)benzo(d) (1,3) dithiole-5,6-diyl)bis-(azanediyl))bis-(meth anylylidene)) (2E,2E')-bis(3-oxobutanoate)] and a highly luminescent connector {TPPE = 1,1,2,2-tetrakis[4-(pyridine-4-yl)phenyl]-ethene}. Complex has a layered structure where the TPPE uses its four diverging pyridines from the TPPE ligand are coordinated by the positions to the flat TTF Schiff-base ligand, and complex has an unprecedented catenation of layers within two interpenetrated frameworks. These coordination polymers reserved the redox activity of the TTF unit. Complex shows gradual spin transition behavior without hysteresis. And the fluorescence intensity of TPPE in changes in tandem with the spin crossover (SCO) transition indicating a possible interplay between fluorescence and SCO behavior.

摘要

通过一种具有氧化还原活性的四硫富瓦烯(TTF)功能化配体[HL = 2,2'-(((2-(4,5-双-(甲硫基)-1,3-二硫醇-2-亚基)苯并(d)(1,3)二硫代-5,6-二亚基)双-(氮杂二亚基))双-(亚甲基))(2E,2E')-双(3-氧代丁酸酯)]和一种高发光连接体{TPPE = 1,1,2,2-四[4-(吡啶-4-基)苯基]-乙烯},得到了两种多晶型铁配位聚合物[FeL(TPPE)]和[(FeL(TPPE))]。配合物具有层状结构,其中TPPE利用其来自TPPE配体的四个发散吡啶通过与扁平TTF席夫碱配体的位置配位,并且配合物在两个互穿框架内具有前所未有的层间连锁。这些配位聚合物保留了TTF单元的氧化还原活性。配合物表现出无滞后的逐渐自旋转变行为。并且在中TPPE的荧光强度与自旋交叉(SCO)转变同步变化,表明荧光和SCO行为之间可能存在相互作用。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5e0a/8365465/64713fb520ef/fchem-09-692939-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5e0a/8365465/95bee2615ee6/fchem-09-692939-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5e0a/8365465/e5a59dca9dd6/fchem-09-692939-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5e0a/8365465/f3641870d2cf/fchem-09-692939-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5e0a/8365465/f60f8c609c48/fchem-09-692939-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5e0a/8365465/92f989c825cd/fchem-09-692939-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5e0a/8365465/64713fb520ef/fchem-09-692939-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5e0a/8365465/95bee2615ee6/fchem-09-692939-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5e0a/8365465/e5a59dca9dd6/fchem-09-692939-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5e0a/8365465/f3641870d2cf/fchem-09-692939-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5e0a/8365465/f60f8c609c48/fchem-09-692939-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5e0a/8365465/92f989c825cd/fchem-09-692939-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5e0a/8365465/64713fb520ef/fchem-09-692939-g005.jpg

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Spin crossover modulation in a coordination polymer with the redox-active bis-pyridyltetrathiafulvalene (pyTTF) ligand.具有氧化还原活性双吡啶四硫富瓦烯(pyTTF)配体的配位聚合物中的自旋交叉调制。
Chem Commun (Camb). 2020 Sep 16;56(72):10469-10472. doi: 10.1039/d0cc03788e. Epub 2020 Aug 7.
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Iron(II) Spin Crossover Complexes Based on a Redox Active Equatorial Schiff-Base-Like Ligand.
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