Selective Construction of Borromean Rings andTweezer‐LikeMolecular Assembly Featuring Cp*Rh/Ir Clips forNear‐InfraredPhotothermal Conversion^†

Abstract

Comprehensive SummaryMaking full use of coordination‐driven self‐assembly strategy, we herein described the selective synthesis of a molecular Borromean rings and two cases of “U”‐shaped tweezer‐like molecular assemblies in high yield by using bipyridyl ligands based on biphenyl unit and half‐sandwich binuclear rhodium(III)/iridium(III) building blocks. The selective synthesis was realized by adjusting the length of dipyridyl arms. The utilization of curved U‐shaped bipyridyl ligand L1 led to tweezer‐like molecular assemblies. Subsequently, olefinic bonds were introduced to elongate dipyridyl arms obtaining ligand L2. The ligand L2 has two stable conformations, U‐shape and Z‐shape, which facilitated the formation of different topologies including the tetranuclear macrocycle and Borromean rings with different building blocks in this work. These structures in solid and solution all have been further confirmed by single‐crystal X‐ray diffraction, NMR analysis, and mass spectrometry. In addition, as an important driving force, π‐π stacking interactions not only played a significant role in the stability of structures but also further triggered photothermal conversion in solution. This research expands the application of topological structures in materials science and provides a new idea for the synthesis of novel photothermal conversion materials.This article is protected by copyright. All rights reserved.

Synthesis and near-infrared photothermal conversion of Cp*Rh-based [2]-catenanes in trapezoidal metallacycles

“…14–18 π–π stacking interactions are among the most important interactions in the chemical self-assembly of interlocked topologies. 19–24 Moreover, these interactions can facilitate nonradiative migration and initiate photothermal conversion. 25–27 While the dependence of the photothermal conversion properties of different self-assembled ensembles on π–π stacking interactions has been documented, the influence of distinct stacking modes on their photothermal conversion efficiency has received limited investigation.…”

Iminopyrrole‐Based Self‐Assembly: A Route to Intrinsically Flexible Molecular Links and Knots

“…The self‐assembly methodology used by Stoddart to construct molecular Borromean rings can be considered a milestone in the field [31–33] . Recently these fascinating molecules were synthesized by coordination‐driven self‐assembly [34–37] . Developments involving Vernier templation [38] and exploitation of alkene metathesis for closing the macrocycle [39–42] opened routes to molecular links and knots of growing complexity.…”

“…[31][32][33] Recently these fascinating molecules were synthesized by coordination-driven self-assembly. [34][35][36][37] Developments involving Vernier templation [38] and exploitation of alkene metathesis for closing the macrocycle [39][40][41][42] opened routes to molecular links and knots of growing complexity.…”

A Coordination-Driven Self-Assembly and NIR Photothermal Conversion Study of Organometallic Handcuffs

“…After the efforts of previous scientists, the synthesis of initial macrocyclic compounds has evolved from [2] catenane compounds to Solomon, Borromean ring and [5] catenane structures, which have been well demonstrated by Sauvage, Stoddart, Fujita and Jin, etc. [14][15][16][17][18][19][20][21][22][23], marking the rapid development of the research field. At the same time, molecular knots and ravel have also experienced a rapid forward process.…”