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首页> 外文期刊>Crystal growth & design >Solid-state N-H?O/O-H?N tautomerism in resonance-assisted 1-(arylazo)-2-naphthols and its through-space π* ← π perturbation in TCNQ cocrystals. A variable-temperature X-ray crystal study
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Solid-state N-H?O/O-H?N tautomerism in resonance-assisted 1-(arylazo)-2-naphthols and its through-space π* ← π perturbation in TCNQ cocrystals. A variable-temperature X-ray crystal study

机译：TCNQ共晶体中共振辅助的1-（芳基偶氮）-2-萘的固态N-H2O / O-H2N互变异构及其通态π*←π扰动。可变温度X射线晶体研究

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摘要

Aryl-substituted 1-arylhydrazo-naphthalen-2-ones and 1-arylazo-naphthalen- 2-ols display ?HN-N=C-C=O??N=N-C=C-OH?ketohydrazone- azoenol prototropic tautomerism in the solid state by forming a strong intramolecular resonance-assisted H-bond (RAHB) that can change from pure N-H?O to pure O-H?N through dynamically disordered N-H?O O-H?N bonds according to the electronic properties of the substituents. The compounds of the series aryl = 4-F-phenyl, 4-CH_3-phenyl, 4-Cl-phenyl, and 1-naphthalenyl and their cocrystals with TCNQ have been studied by X-ray crystallography at temperatures varying from 100 to 295 K. The packing is extensively discussed in terms of charge-transfer (CT) or electron donor-acceptor (EDA) interactions, showing that the herringbone packing of pure azonaphthols and the columnar one of their TCNQ cocrystals are respectively determined by specific σ* ← π and π* ← π interactions. It is shown that cocrystallization with TCNQ induces two main effects: (i) in TCNQ itself, a significant change from quinoid to aromatic geometry, from which a CT of some 0.40 e can be estimated; (ii) in azonaphthols, a shift of the N-H?O N?H-O equilibrium toward the pure N-H?O tautomer, accompanied by a decrease of π-delocalization inside the conjugated?HN-N=C-C=O?resonant fragment. These findings suggest that through-space effects caused by TCNQ cocrystallization on the RAHB equilibrium are formally equivalent to through-bond effects caused by the aryl substituents.
机译：芳基取代的1-芳基偶氮-萘-2-酮和1-芳基偶氮-萘-2-醇在固态下显示出？HN-N = CC = O ?? N = NC = C-OH？酮hydr-偶氮烯醇质子互变异构通过形成强分子内共振辅助氢键（RAHB），可以根据取代基的电子性质通过动态无序的NH 2 O OH 3 N键从纯NH 2 O变为纯OH 2N。已通过X射线晶体学在100至295 K的温度范围内研究了芳基= 4-F-苯基，4-CH_3-苯基，4-Cl-苯基和1-萘基系列化合物及其与TCNQ的共晶体。根据电荷转移（CT）或电子供体-受体（EDA）相互作用对堆积进行了广泛的讨论，表明纯氮杂萘酚及其柱状TCNQ共晶体之一的人字形堆积分别由特定的σ*←π确定。和π*←π相互作用。结果表明，与TCNQ共结晶会引起两个主要影响：（i）在TCNQ本身中，从醌型到芳族几何结构有显着变化，据此CT约为0.40 e; （ii）在偶氮酚中，N-H 2 O N 2 H-O平衡向纯的N-H 2 O互变异构体转移，伴随着在共轭αHN-N ＝ C-C ＝ O 2共振片段内π-离域的减少。这些发现表明，TCNQ共结晶对RAHB平衡造成的贯穿空间效应在形式上等同于芳基取代基引起的贯穿键效应。

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