在柔性环状膦配体上模板化的双核金（I）膦炔基配合物：合成和固态发光的一些特征。,Inorganic Chemistry

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在柔性环状膦配体上模板化的双核金（I）膦炔基配合物：合成和固态发光的一些特征。
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2019-12-09 , DOI: 10.1021/acs.inorgchem.9b02091
Igor D Strelnik ₁ , Vladimir V Sizov ₂ , Vladislav V Gurzhiy ₃ , Alexei S Melnikov ₄ , Ilya E Kolesnikov ₅ , Elvira I Musina ₁ , Andrey A Karasik ₁ , Elena V Grachova ₂

Affiliation

柔性双齿环状膦，即1,5-双（对甲苯基）-3,7-双（吡啶-2-基）-1,5-二氮杂3,7-二磷酸环辛烷（PNNP）被用作模板以构建双核杂多膦膦炔基络合物家族[PNNP（AuC2R）2]，R = Ph，C6H10OH，C5H8OH，（CH3）2COH，Ph2COH。通过CHN元素分析，NMR光谱和单晶X射线分析对所有获得的配合物进行表征。发现金（I）配合物表现出不同的晶体结构组织，这取决于共结晶溶剂（二氯甲烷，丙酮和乙腈）的性质，这是因为通过氢键形成了超分子配合物。这些弱相互作用似乎决定构象，堆积，在光物理性质中反映的柔性复杂分子的空间和空间合作，已在溶液和固态下进行了仔细研究。该配合物在室温下显示出溶液中的弱发射，并且冻结导致发射的蓝移，其伴随着发光强度的显着增加。从二氯甲烷中分离出来的所有金（I）配合物在固态下均显示绿色磷光，R = Ph和Ph2COH的配合物分别在从丙酮和乙腈中重结晶后，其发射色显着变化，这表明其本身是一种显着的红移最大可达120 nm。

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Binuclear Gold(I) Phosphine Alkynyl Complexes Templated on a Flexible Cyclic Phosphine Ligand: Synthesis and Some Features of Solid-State Luminescence.

A flexible bidentate cyclic phosphine, namely, 1,5-bis(p-tolyl)-3,7-bis(pyridin-2-yl)-1,5-diaza-3,7-diphosphacyclooctane (PNNP), was used as a template to construct a family of binuclear heteroleptic phosphine alkynyl complexes [PNNP(AuC2R)2], with R = Ph, C6H10OH, C5H8OH, (CH3)2COH, Ph2COH. All complexes obtained were characterized by CHN elemental analysis, NMR spectroscopy, and single-crystal X-ray analysis. It was found that the gold(I) complexes demonstrate a different organization of the crystal structure depending on the nature of the cocrystallized solvent (dichloromethane, acetone, and acetonitrile) because of formation of the supramolecular complexes through hydrogen bonding. These weak interactions appear to determine the conformation, packing, and spatial cooperation of flexible complex molecules that are reflected in the photophysical properties, which were carefully investigated in solution and in the solid state. The complexes demonstrate weak emission in solution at room temperature, and freezing results in blue shifting of the emission, which is accompanied by a significant increase in the luminescence intensity. Being isolated from dichloromethane, all gold(I) complexes exhibit green phosphorescence in the solid state, and the complexes with R = Ph and Ph2COH display substantial variation of their emission color after recrystallization from acetone and acetonitrile, respectively, which manifests itself as a significant bathochromic shift of up to 120 nm. The structural nonrigidity of the gold(I) complexes obtained and its impact on the properties of low-energy excited states were investigated in detail by density functional theory calculations, which indicate the significant role of the structural flexibility of the PNNP ligand in the formation of the low-energy excited states and confirm the impact of rotation of the functional groups in the coordination sphere on the emission properties of complexes.

更新日期：2019-12-09

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