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Synthesis, structure and photophysical properties of two tetranuclear copper(I) iodide complexes based on acetylpyridine and diphosphine mixed ligands
Acta Crystallographica Section C ( IF 0.7 ) Pub Date : 2021-01-06 , DOI: 10.1107/s2053229620016745 Bing-Jun Cao , Ran Li , Xi-He Huang
Acta Crystallographica Section C ( IF 0.7 ) Pub Date : 2021-01-06 , DOI: 10.1107/s2053229620016745 Bing-Jun Cao , Ran Li , Xi-He Huang
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Two copper(I) iodide tetramers, namely, [μ2‐1,3‐bis(diphenylphosphanyl)propane‐κ2P:P′]di‐μ3‐iodido‐di‐μ2‐iodido‐[1‐(pyridin‐3‐yl)ethan‐1‐one‐κN]tetracopper(I) dichloromethane disolvate, [Cu4I4(C6H7NO)2(C27H26P2)2]·2CH2Cl2 (CuL3), and [μ2‐1,3‐bis(diphenylphosphanyl)propane‐κ2P:P′]di‐μ3‐iodido‐di‐μ2‐iodido‐[1‐(pyridin‐4‐yl)ethan‐1‐one‐κN]tetracopper(I), [Cu4I4(C6H7NO)2(C27H26P2)2] (CuL4), have been synthesized from reactions of CuI, 1,3‐bis(diphenylphosphanyl)propane (dppp) and 3‐ or 4‐acetylpyridine (3/4‐acepy). The complexes were characterized by elemental analysis, IR spectroscopy, single‐crystal X‐ray diffraction (XRD), powder XRD and photoluminescence spectroscopy. Both complexes possess a stair‐step [Cu4I4] cluster structure with a crystallographic inversion centre located in the middle of a Cu2I2 ring (Z′ = 
). The dppp ligands each adopt a bidentate coordination mode that bridges two CuI centres on one side of the [Cu4I4] cluster and the acepy ligands act as terminal ligands. The solid‐state samples of similar complexes show highly efficiency thermally activated delayed fluorescence (TADF) at room temperature. At ambient temperature, both CuL3 and CuL4 exhibit photoluminescence, with a maximum emission in the region 560–580 nm and with short emissive decay times, but only phosphorescence was observed at 77 K. The narrow gaps between the higher lying singlet state and the triplet state, ΔE(S1 − T1), also confirm the presence of TADF. Structure analysis and consideration of photoluminescence indicates that the position of the acetyl group on the heterocyclic ligand has an obvious influence on the structural arrangement, on intermolecular interactions and on the observed photophysical properties.
中文翻译：
基于乙酰吡啶和二膦混合配体的两种四核碘化亚铜（I）配合物的合成，结构和光物理性质
两个铜（I），碘化四聚体，即，[μ 2 -1,3-双（二苯基膦）丙烷κ 2 P：P ']二μ 3 -iodido二- μ 2 -iodido- [1-（吡啶-3-（3-基）乙-1-酮-N ]四铜（I）二氯甲烷二溶剂化物，[Cu 4 I 4（C 6 H 7 NO）2（C 27 H 26 P 2）2 ]·2CH 2 Cl 2（铜大号3）和[μ 2 -1,3-双（二苯基膦）丙烷κ 2 P：P ']二μ 3 -iodido二- μ 2 -iodido- [1-（吡啶-4-基）乙-1-酮-κ Ñ ] tetracopper（I），[铜4我4（C 6 H 7 NO）2（C 27 H 26 P 2）2 ]（Cu L 4），是由CuI，1,3-双（二苯基膦基）丙烷（dppp）和3-或4-乙酰基吡啶（3 / 4-acepy）。通过元素分析，红外光谱，单晶X射线衍射（XRD），粉末XRD和光致发光光谱对复合物进行表征。两种配合物均具有阶梯形[Cu 4I 4 ]的簇结构具有位于Cu 2 I 2环（Z '=）中间的晶体学反转中心。dppp配体各自采用双齿配位模式，该模式在[Cu 4 I 4 ]簇的一侧桥接两个Cu I中心，而acepy配体充当末端配体。相似配合物的固态样品在室温下显示出高效的热活化延迟荧光（TADF）。在环境温度下，Cu L 3和Cu L 4均表现出光致发光，但与在77K仅观察到磷光该区域560-580纳米，并用短的发射衰减时间的最大发射，较高躺在单重态和三重态，Δ之间的窄的间隙ë（小号1 - T 1），也要确认TADF的存在。结构分析和光致发光的考虑表明，杂环配体上乙酰基的位置对结构排列，分子间相互作用和观察到的光物理性质有明显影响。
更新日期：2021-02-04
). The dppp ligands each adopt a bidentate coordination mode that bridges two CuI centres on one side of the [Cu4I4] cluster and the acepy ligands act as terminal ligands. The solid‐state samples of similar complexes show highly efficiency thermally activated delayed fluorescence (TADF) at room temperature. At ambient temperature, both CuL3 and CuL4 exhibit photoluminescence, with a maximum emission in the region 560–580 nm and with short emissive decay times, but only phosphorescence was observed at 77 K. The narrow gaps between the higher lying singlet state and the triplet state, ΔE(S1 − T1), also confirm the presence of TADF. Structure analysis and consideration of photoluminescence indicates that the position of the acetyl group on the heterocyclic ligand has an obvious influence on the structural arrangement, on intermolecular interactions and on the observed photophysical properties.
中文翻译：
基于乙酰吡啶和二膦混合配体的两种四核碘化亚铜（I）配合物的合成，结构和光物理性质
两个铜（I），碘化四聚体，即，[μ 2 -1,3-双（二苯基膦）丙烷κ 2 P：P ']二μ 3 -iodido二- μ 2 -iodido- [1-（吡啶-3-（3-基）乙-1-酮-N ]四铜（I）二氯甲烷二溶剂化物，[Cu 4 I 4（C 6 H 7 NO）2（C 27 H 26 P 2）2 ]·2CH 2 Cl 2（铜大号3）和[μ 2 -1,3-双（二苯基膦）丙烷κ 2 P：P ']二μ 3 -iodido二- μ 2 -iodido- [1-（吡啶-4-基）乙-1-酮-κ Ñ ] tetracopper（I），[铜4我4（C 6 H 7 NO）2（C 27 H 26 P 2）2 ]（Cu L 4），是由CuI，1,3-双（二苯基膦基）丙烷（dppp）和3-或4-乙酰基吡啶（3 / 4-acepy）。通过元素分析，红外光谱，单晶X射线衍射（XRD），粉末XRD和光致发光光谱对复合物进行表征。两种配合物均具有阶梯形[Cu 4I 4 ]的簇结构具有位于Cu 2 I 2环（Z '=
）中间的晶体学反转中心。dppp配体各自采用双齿配位模式，该模式在[Cu 4 I 4 ]簇的一侧桥接两个Cu I中心，而acepy配体充当末端配体。相似配合物的固态样品在室温下显示出高效的热活化延迟荧光（TADF）。在环境温度下，Cu L 3和Cu L 4均表现出光致发光，但与在77K仅观察到磷光该区域560-580纳米，并用短的发射衰减时间的最大发射，较高躺在单重态和三重态，Δ之间的窄的间隙ë（小号1 - T 1），也要确认TADF的存在。结构分析和光致发光的考虑表明，杂环配体上乙酰基的位置对结构排列，分子间相互作用和观察到的光物理性质有明显影响。
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