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Title: Self-passivation of Halide Interstitial Defects by Organic Cations in Hybrid Lead-Halide Perovskites: Ab Initio Quantum Dynamics
Award ID(s):
2154367
PAR ID:
10583511
Author(s) / Creator(s):
; ; ; ; ;
Publisher / Repository:
ACS Publications
Date Published:
Journal Name:
Journal of the American Chemical Society
Volume:
146
Issue:
42
ISSN:
0002-7863
Page Range / eLocation ID:
29255 to 29265
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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  1. We present a combined experimental and density functional theory study that characterizes the charge and spin density in NiX2(3,5-lutidine)4(X= Cl, Br and I). In this material, magnetic exchange interactions occur via Ni2+–halide...halide–Ni2+pathways, forming one-dimensional chains. We find evidence for weak halide...halide covalency in the iodine system, which is greatly reduced whenX= Br and is absent forX= Cl; this is consistent with the reported `switching-on' of magnetic exchange in the larger-halide cases. Our results are benchmarked against density functional theory calculations on [NiHF2(pyrazine)2]SbF6, in which the primary magnetic exchange is mediated by F–H–F bridging ligands. This comparison indicates that, despite the largely depleted charge density found at the centre of halide...halide bonds, these through-space interactions can support strong magnetic exchange gated by weak covalency and enhanced by significant electron density overlapping that of the transition metal centres. 
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