High‐pressure‐induced phase transition in 1,3‐diphenylurea: The approaching of N–H⋯O hydrogen‐bonded chains

Abstract

The crystal structure and hydrogen‐bonded chains of 1,3‐diphenylurea were found to have abrupt changes when the pressure increased to 1.8 GPa. Based on Raman spectra, the intermolecular interactions, the vibrations of chemical groups, and the molecular conformation were clearly distinguished from the initial state. The anisotropic compression of the original crystal structure and the occurrence of structural phase transition were confirmed by the results of in situ high‐pressure synchrotron X‐ray diffraction experiments. The new phase was stable up to about 10.0 GPa. The inevitable creasing of the N–H⋯O hydrogen‐bonded chains was derived from the remarkable shrink of distance between hydrogen‐bonded chains, which can be treated as the main reason leading to this phase transition. The first‐principle calculations and Hirshfeld surfaces further confirmed the analysis of the experimental results. This study demonstrates that excessively reducing the space between of hydrogen‐bonded chains will rearrange the self‐assembly of supramolecular materials.

Neutral 1D Perovskite‐Type ABX3 Phase Transition Material with a Narrowband Emission and Semiconductor Property

“…[19],[20] We studied further in the exploded view of the fingerprint (Figure 6). Obviously, the ratios of H…Br interactions occupy the 43.5% of the total hirshfeld surface in 1‐LTP , but 1‐RTP is 36.8%, this phenomenon indicates an increase in the hydrogen bond interaction among the inorganic chain and organic cation [21] . For example, the spike marked with a red circle extends from (d i , d e )=(0.9, 1.7) to (0.8, 1.5) during the cooling process, this spike is inferred from Table S2 and S3 to be related to O−H…Br hydrogen bond [22] .…”

“…Obviously, the ratios of H…Br interactions occupy the 43.5% of the total hirshfeld surface in 1-LTP, but 1-RTP is 36.8%, this phenomenon indicates an increase in the hydrogen bond interaction among the inorganic chain and organic cation. [21] For example, the spike marked with a red circle extends from (d i , d e ) = (0.9, 1.7) to (0.8, 1.5) during the cooling process, this spike is inferred from Table S2 and S3 to be related to OÀ H…Br hydrogen bond. [22] Combined with the previous structural analysis, it can be inferred that the change of hydrogen bond is also an important factor in the occurrence of phase transition.…”

Tunable hybrid perovskites with a narrow bandgap and multistage phase transition properties: 2,2-difluoroethylamine·antimony hexabromide

“…The hydrogen bond, H⋯Br, depicts a sharp peak in the fingerprint plot. 31 The 2D fingerprint plot revealed that the highest contribution was from the H⋯Br interaction (51.0%) at T tr -1. However, with an increase in temperature, the contribution of the H⋯Br interaction decayed to 43.9% at T tr -2, and finally, to 5.9% at T tr -3.…”

Recent advances in linear and nonlinear Raman spectroscopy. Part XIV

“…Dai et al [ 178 ] described the high‐pressure‐induced phase transition in 1,3‐diphenylurea by considering the spatial approach of N‐H…O hydrogen‐bonded chains. Their study demonstrates that excessively reducing the space between hydrogen‐bonded chains will rearrange the self‐assembly of supramolecular materials.…”