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一种用于包封富勒烯的基于碗烯的金属盒。

A corannulene-based metallobox for the encapsulation of fullerenes.

作者信息

Ibáñez Susana, Mejuto Carmen, Cerón Katherin, Sanz Miguel Pablo J, Peris Eduardo

机构信息

Institute of Advanced Materials (INAM), Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universitat Jaume I Av. Vicente Sos Baynat s/n Castellón E-12071 Spain

Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Universidad de Zaragoza-CSIC 50009 Zaragoza Spain.

出版信息

Chem Sci. 2024 Jul 16;15(33):13415-13420. doi: 10.1039/d4sc03661a. eCollection 2024 Aug 22.

DOI:10.1039/d4sc03661a
PMID:39183911
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11339943/
Abstract

A corannulene-bis-N-imidazolium salt was used for the synthesis of two corannulene-bis-N-heterocyclic carbenes of dirhodium(i) complexes of formula (corannulene-di-NHC)[RhCl(COD)] and (corannulene-di-NHC)[RhCl(CO)]. Both complexes were characterized by spectroscopic techniques, and the electron-donating properties of the corannulene-di-NHC ligand were studied by means of infrared spectroscopy and cyclic voltammetry. The complex (corannulene-di-NHC)[RhCl(COD)] was used for the encapsulation of fullerenes C and C, generating host-guest complexes with 2 : 1 stoichiometry, as evidenced by H NMR and ITC titrations. Then, a tetra-rhodium(i) metallo-rectangle supported by two corannulene-bis-imidazolylidene ligands and two cofacial 4,4'-bipyridine ligands was prepared and characterized. This metallobox is capable of quantitatively encapsulating fullerenes C and C, forming complexes that are highly stable even at high temperatures. The molecular structure of the metallobox with encapsulated C reveals a perfect size and shape complementarity that benefits from the concave-convex π-π interaction between the polyaromatic surfaces of the host and the guest.

摘要

一种碗烯 - 双 - N - 咪唑鎓盐被用于合成两种式为（碗烯 - 双 - NHC）[RhCl(COD)]和（碗烯 - 双 - NHC）[RhCl(CO)]的二铑（I）配合物的碗烯 - 双 - N - 杂环卡宾。两种配合物均通过光谱技术进行了表征，并通过红外光谱和循环伏安法研究了碗烯 - 双 - NHC配体的供电子性质。配合物（碗烯 - 双 - NHC）[RhCl(COD)]被用于包封富勒烯C和C，通过1H NMR和ITC滴定证明生成了化学计量比为2∶1的主客体配合物。然后，制备并表征了一种由两个碗烯 - 双 - 咪唑亚基配体和两个共面的4,4'-联吡啶配体支撑的四铑（I）金属矩形。这种金属盒能够定量包封富勒烯C和C，形成即使在高温下也高度稳定的配合物。包封有C的金属盒的分子结构揭示了完美的尺寸和形状互补性，这得益于主体和客体的多芳族表面之间的凹凸π - π相互作用。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f1d/11339943/855d22d21a49/d4sc03661a-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f1d/11339943/a27de01c3242/d4sc03661a-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f1d/11339943/15ff0bcfd529/d4sc03661a-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f1d/11339943/c1f54748f45d/d4sc03661a-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f1d/11339943/e34895bff7ff/d4sc03661a-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f1d/11339943/29f187d490ba/d4sc03661a-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f1d/11339943/855d22d21a49/d4sc03661a-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f1d/11339943/a27de01c3242/d4sc03661a-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f1d/11339943/15ff0bcfd529/d4sc03661a-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f1d/11339943/c1f54748f45d/d4sc03661a-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f1d/11339943/e34895bff7ff/d4sc03661a-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f1d/11339943/29f187d490ba/d4sc03661a-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f1d/11339943/855d22d21a49/d4sc03661a-f4.jpg

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