Copper(I) halide cluster-based coordination polymers modulated by chiral ditopic dithiodianthranilide ligands: synthesis, crystal structure and photoluminescence,CrystEngComm

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Copper(I) halide cluster-based coordination polymers modulated by chiral ditopic dithiodianthranilide ligands: synthesis, crystal structure and photoluminescence
CrystEngComm ( IF 2.6 ) Pub Date : 2020-11-06 , DOI: 10.1039/d0ce01589j
Jarosław Chojnacki _{1,

2,

3,

4} , Michał Mońka _{4,

5,

6,

7,

8} , Illia E. Serdiuk _{4,

5,

6,

7,

8} , Piotr Bojarski _{4,

5,

6,

7,

8} , Tadeusz Połoński _{1,

2,

3,

4} , Teresa Olszewska _{1,

2,

3,

4}

Affiliation

Reaction of copper(I) halides with chiral dithiodianthranilides mdta and bdta afforded polymeric complexes where polynuclear CuX clusters were linked together by ditopic bridging ligands into 1D chains or 2D layer structures. In the case of racemic ligands double stranded chain polymers were formed where the Cu₄X₄ (X = I or Br) cores are connected by enantiomeric pairs of the ditopic ligands. In contrast, a homochiral mdta ligand created a single stranded hybrid chain involving single mdta enantiomers and solvated Cu₅I₅ clusters or 2D square (4,4) nets composed of rings comprising four Cu₃X₃ clusters in nodes and four homochiral ligand molecules in sides with solvent MeCN molecules between the grid layers. The hybrid layer structure obtained from CuCl and the racemic mdta ligand crystallized as a conglomerate that led to its self-resolution into enantiomeric chiral crystals. The solid state CD spectra revealed contribution of two electronic transitions to the diffuse lowest energy absorption band of the complexes. In addition the observed long wavelength Cotton effect sign reflected the helicity of the thiobenzamide chromophore in the ligand unit. At room temperature the solid complexes exhibited weak red phosphorescence near 600–620 nm. Upon cooling down to 10 K all investigated complexes are phosphorescent with average lifetimes of 17–84 μs.

中文翻译：

卤化铜（I）簇基配位聚合物，由手性二位二硫代双邻苯二胺配体调节：合成，晶体结构和光致发光

卤化铜（I）与手性二硫代双苯胺化物mdta和bdta的反应提供了聚合物络合物，其中多核CuX簇通过对位桥接配体连接到1D链或2D层结构中。在外消旋配体的情况下，形成了双链聚合物，其中Cu ₄ X ₄（X = I或Br）核通过对位配体的对映体对连接。相反，同手性的mdta配体产生了一条单链杂合链，涉及单mdta对映异构体和溶剂化的Cu ₅ I ₅簇或由包含四个Cu ₃的环组成的2D正方形（4,4）网X ₃簇集结，侧面有四个同手性配体分子，网格层之间有溶剂MeCN分子。由CuCl和外消旋的mdta配体获得的杂化层结构结晶为团块，导致其自拆分为对映体手性晶体。固态CD光谱揭示了两个电子跃迁对复合物的最低扩散能量吸收带的贡献。另外，观察到的长波长棉效应信号反映了配体单元中硫代苯甲酰胺发色团的螺旋度。在室温下，固体络合物在600–620 nm附近显示出弱红色荧光。冷却至10 K后，所有研究的络合物均为磷光，平均寿命为17–84μs。

更新日期：2020-11-25

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