Hydrogen-Bonding-Induced H-Aggregation of Charge-Transfer Complexes for Ultra-Efficient Second Near-Infrared Region Photothermal Conversion  

作　　者：Jieqiong Xu Zhiwei Yin Liang Zhang Qian Dong Xinqi Cai Shengkai Li Qian Chen Phouphien Keoingthong Zhaoqian Li Long Chen Zhuo Chen Weihong Tan 

机构地区：[1]Molecular Science and Biomedicine Laboratory,State Key Laboratory of Chemo/Biosensing and Chemometrics,College of Chemistry and Chemical Engineering,College of Life Sciences,Hunan Provincial Key Laboratory of Biomacromolecular Chemical Biology,Hunan University,Changsha,Hunan 410082 [2]Faculty of Science and Technology,University of Macao,Avenida da Universidade,Taipa 999078 [3]The Cancer Hospital of the University of Chinese Academy of Sciences(Zhejiang Cancer Hospital),Institute of Basic Medicine and Cancer(IBMC),Chinese Academy of Sciences,Hangzhou,Zhejiang 310022

出　　处：《CCS Chemistry》2022年第7期2333-2343,共11页中国化学会会刊（英文）

基　　金：financially supported by the National Natural Science Foundation of China(grant nos.91953000 and 21827811);the Science and Technology Innovation Program of Hunan Province(grant nos.2019SK2201 and 2020RC4017);the Science and Technology Development Fund,Macao(grant no.196/2017/A3).

摘　　要：Aggregation plays a critical role in modulating the photophysical process of organicmolecules.However,the rational control of the construction of a functionoriented stacking mode for efficient photothermal(PT)conversion in the second near-infrared region(NIR-II;1000-1700 nm)remains a challenge.Herein,an H-aggregation of 3,3′,5,5′-Tetramethylbenzidine(TMB)-TMB dication(TMB++)complexes in linear agarose(H-TTC/LAG)with narrowed band gap(0.96 eV)was fabricated through intermolecular hydrogenbonding interactions between the amino groups of TTC and the peripheral hydroxyl groups of LAG.Charge-transfer mechanism and H-aggregation ensured NIR-Ⅱ absorption of the complex at>1400 nm.The H-aggregation also promoted a non-radiation relaxation pathway and improved the thermal stability of TTC,which together favored the constructed H-TTC/LAG with ultra-efficient PT conversion that increased rapidly to 140℃ in 15 s under the NIR-Ⅱ laser(1064 nm,1.0 W cm^(−2))irradiation.Such a unique H-TTC/LAG with good biocompatibility was used to demonstrate a superior PT therapy via high-efficie ncy tumor growth inhibition in mouse mammary carcinoma(4T1)the BALB/c mice tumor-bearing xenografts.This is the first established H-aggregation of charge-transfer complexes in a noncovalent system,which not only provides a new strategy to develop ultra-efficient NIR-Ⅱ PT materials but also paves the way for constructing functional materials with aggregates of charge-transfer complexes.

关 键 词：aggregation charge transfer hydrogen bonding NIR-Ⅱ photothermal conversion 

分 类 号：O62[理学—有机化学]