Spatial, Hysteretic, and Adaptive Host-Guest Chemistry in a Metal-Organic Framework with Open Watson-Crick Sites

• Published in: Angewandte Chemie International Edition Vol. 54; no. 36; pp. 10454 - 10459
• Main Authors: Cai, Hong, Li, Mian, Lin, Xiao-Rong, Chen, Wei, Chen, Guang-Hui, Huang, Xiao-Chun, Li, Dan
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.09.2015; WILEY‐VCH Verlag; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: adaptive chemistry; Adenine; Adenines; Benzene; Binding; Chemisorption; Constraints; Crystal structure; Deoxyribonucleic acid; DNA; DNA - chemistry; host-guest chemistry; Hysteresis; Kinetics; Metal-organic frameworks; Metals - chemistry; Organic Chemicals - chemistry; Porosity; Protein folding; Recognition; Spectrophotometry, Infrared; Spectrum Analysis, Raman; Supramolecular compounds; supramolecular recognition; Surface chemistry; Thermodynamics; Thymine; Watson-Crick base pairing; supramolecular recognition; adaptive chemistry; host-guest chemistry; Watson-Crick base pairing; metal-organic frameworks
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201502045

Biological and artificial molecules and assemblies capable of supramolecular recognition, especially those with nucleobase pairing, usually rely on autonomous or collective binding to function. Advanced site‐specific recognition takes advantage of cooperative spatial effects, as in local folding in protein–DNA binding. Herein, we report a new nucleobase‐tagged metal–organic framework (MOF), namely ZnBTCA (BTC=benzene‐1,3,5‐tricarboxyl, A=adenine), in which the exposed Watson–Crick faces of adenine residues are immobilized periodically on the interior crystalline surface. Systematic control experiments demonstrated the cooperation of the open Watson–Crick sites and spatial effects within the nanopores, and thermodynamic and kinetic studies revealed a hysteretic host–guest interaction attributed to mild chemisorption. We further exploited this behavior for adenine–thymine binding within the constrained pores, and a globally adaptive response of the MOF host was observed. A global affair: A metal–organic framework (MOF) in which adenine residues with their Watson–Crick face exposed were immobilized periodically on the interior crystalline surface showed cooperativity between the open Watson–Crick sites and spatial effects within the nanopores. When this behavior was exploited for adenine–thymine binding within the constrained pores (see picture), a globally adaptive response of the MOF host was observed.