文献类型：期刊文献

英文题名：Polymorph-triggered multiple responses in dynamic molecular crystals of barbituric acid derivatives

作者：Sun, Ya-Bing[1,2];Liu, Jiang-Tao[1,2];Lin, Hui-Yao[1,2];Zhang, Chen-Chen[1,2];Qu, Da-Hui[1,2];Tong, Fei[1,2]

机构：[1]East China Univ Sci & Technol, Key Lab Adv Mat, 130 Meilong Rd, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Inst Fine Chem, Feringa Nobel Prize Scientist Joint Res Ctr,Sch Ch, Frontiers Sci Ctr Materiobiol & Dynam Chem,Joint I, Meilong Rd 130, Shanghai 200237, Peoples R China

年份：2026

外文期刊名：JOURNAL OF MATERIALS CHEMISTRY C

收录：;EI(收录号：20260920191928);WOS:【SCI-EXPANDED(收录号:WOS:001703557000001)】；

基金：This work was supported by the National Natural Science Foundation of China (22375063, 22405089, 22220102004), Science and Technology Commission of Shanghai Municipality (23JC1401700, 24DX1400200), the Innovation Program of Shanghai Municipal Education Commission (2023ZKZD40), China National Petroleum Corporation (CNPC) Innovation Found (2024DQ02-0410), the Programme of Introducing Talents of Discipline to Universities (B16017), and the Fundamental Research Funds for the Central Universities. The authors thank Research Center of Analysis and Test of East China University of Science and Technology for the help on the characterization.

语种：英文

外文关键词：Conformations - Crystalline materials - Crystals - Derivatives - Hydrogen - Hydrogen bonds - Molecules - Photochromism - Polymorphism

摘要：Achieving controllable, dynamic polymorphism and integrated multi-stimuli responses in rigid organic molecules without flexible molecular regulators is challenging. This work reports four polymorphs (Forms A, B, C, and D) of (E)-NAPT, a rigid, conjugated molecule constructed from a barbituric acid moiety and a naphthalene unit, linked by a divinyl linker. Our findings demonstrate that the crystallization environment dictates the hydrogen-bonding saturation state of the terminal barbituric acid units, forcing the backbone to transition from planar to bent and dictating distinct packing modes. Form A adopts a layered packing stabilized by a water molecule-bridged saturated hydrogen-bonding network. In contrast, Form D maintains a saturated hydrogen-bonding motif but lacks stress-relieving water molecules, leading to a trigonal pyramidal packing. Forms B and C exhibit comparable one-dimensional hydrogen-bonding arrays assembled via offset head-to-head stacking. These structural variations directly encode multi-stimuli responsiveness. Heating transforms Form A into Form D via dehydration with a fluorescence switch, a process reversible by solvent vapor. Form B displays dual pathways: conversion to Form A via vapor or irreversible thermal transition to Form C, triggering macroscopic mechanical motions. This conformational bending within the rigid framework also translates to their photoresponsive properties. In Form A, the plane conformation provides the reactive sites with ideal parallel alignment and proximity, enabling reversible photochromism. This work elucidates that manipulating molecular conformational strain by tuning the hydrogen-bonding networks effectively "encodes" complex phase-transition pathways and multi-stimuli responsiveness into rigid molecular frameworks, offering a new paradigm for the rational design of dynamic crystalline materials.