四（4-吡啶基）卟啉超分子构件中的结构多样性,Crystal Growth & Design

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四（4-吡啶基）卟啉超分子构件中的结构多样性
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2019-04-19 00:00:00 , DOI: 10.1021/acs.cgd.9b00399
Manish Kumar Mishra ₁ , Hemant Choudhary ₁ , David B. Cordes ₁ , Steven P. Kelley ₂ , Robin D. Rogers _{1,

3}

Affiliation

为了纪念晶体工程的先驱以色列·戈德伯格教授，我们报告了一系列基于配体四（4-吡啶基）卟啉（TPyP）的新型骨架固体。在环境温度下，TPyP与七种不同的金属盐在液-液扩散下的自发反应表明，由于构象自由度增加，离子化合物的形成比配位聚合物更可取。{{HgI ₂）₂（TPyP ）} _n ·4 n CHCl ₃ ·2 n TCE（TCE = 1,1,2,2-四氯乙烷）和{（Ba（μ1,1-NCS）（ μ1,1,3-NCS）（H ₂ O）（MeCN））₂（TPyP）} _n ·4 n H ₂O显示出已知的[（HgI ₂）₂（TPyP ）] _∞聚合物基序的新异构体形式，以及通过氢键键合到三维锰矿（mog）网中的二维蜂窝状聚合物基序。四种质子化的卟啉盐，[H ₃ TPyP] [PF ₆ ] ₃ ·0.5TCE，[H ₂ TPyP ] [I ₃ ] ₂ ·2MeOH，[H ₄ TPyP ] [UO ₂ Cl ₄ ] ₂ ·6MeCN和[H ₄ TPyP] [Th（NO ₃）₆ ] [NO ₃ ] ₂观察到哪个氢键给出一维或二维网络，或者在[H ₄ TPyP] [UO ₂ Cl ₄ ] ₂ ·6MeCN的情况下，观察到离散的双核氢键配合物。在一种情况下，是中性的氢键络合物Ce（NO ₃）₃（MeOH）₃（H ₂ O）·TPyP·TCE·H ₂形成O，采用面心立方（fcc）网络的三维自渗透变体。这些新结构代表了有机-无机杂化晶体化合物，其中具有氢键和配位功能的多齿卟啉单元通过无机连接器相互连接成自组装的三维结构。这项工作显示了非共价键与配位网络的相对稳定性，以及在存在或不存在配位离子作为接头的情况下TPyP构件构建超分子组装体的有效潜力。

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Structural Diversity in Tetrakis(4-pyridyl)porphyrin Supramolecular Building Blocks

In memory of a pioneer in crystal engineering, Prof. Israel Goldberg, we report a series of new framework solids, based on the ligand tetrakis(4-pyridyl)porphyrin (TPyP). Spontaneous reactions of TPyP with seven different metal salts under liquid–liquid diffusion at ambient temperature show that the formation of ionic compounds is preferred to coordination polymers due to increased conformational freedom. Two coordination networks, {(HgI₂)₂(TPyP)}_n·4nCHCl₃·2nTCE (TCE = 1,1,2,2-tetrachloroethane), and {(Ba(μ1,1-NCS)(μ1,1,3-NCS)(H₂O)(MeCN))₂(TPyP)}_n·4nH₂O, displayed a new isomeric form of the known [(HgI₂)₂(TPyP)]_∞ polymeric motif, and a two-dimensional honeycomb polymeric motif linked by hydrogen bonding into a three-dimensional moganite (mog) net, respectively. Four protonated porphyrinic salts, [H₃TPyP][PF₆]₃·0.5TCE, [H₂TPyP][I₃]₂·2MeOH, [H₄TPyP][UO₂Cl₄]₂·6MeCN, and [H₄TPyP][Th(NO₃)₆][NO₃]₂, were observed which hydrogen bond to give one- or two-dimensional networks, or in the case of [H₄TPyP][UO₂Cl₄]₂·6MeCN, a discrete dinuclear hydrogen-bonded complex. In one case, a neutral, hydrogen-bonded complex, Ce(NO₃)₃(MeOH)₃(H₂O)·TPyP·TCE·H₂O, was formed which adopts a three-dimensional, self-penetrated variant of the face-centered cubic (fcc) network. These new structures represent hybrid organic–inorganic crystalline compounds in which the multidentate porphyrin units, having both hydrogen bonding, as well as coordination functionalities, are interlinked through the inorganic connectors into self-assembled three-dimensional architectures. This work shows the relative stability of noncovalently bound versus coordination networks as well as the effective potential of the TPyP building block to construct supramolecular assemblies in the presence or absence of coordinating ions as linkers.

更新日期：2019-04-19

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