Intermolecular Hydrogen-Bonding Correlated Structure Distortion and Broadband White-Light Emission in 5-Ammonium Valeric Acid Templated Lead Chloride Perovskites

Yang, Wantian; He, Huanfeng; Tong, Guoliang; Hu, Jiarui; Xiao, Xiong; Chen, Junnian; Li, Mingkai; He, Yunbin

doi:10.1021/acs.cgd.1c00566

Cited by 14 publications

(20 citation statements)

References 31 publications

(56 reference statements)

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“…The structure of [HOOC(CH 2 ) 4 NH 3 ] 2 PbCl 4 features virtually similar intermolecular bonding at the interface region between the halides and the ammonium head ( Figure 22 c,d). The N–H···Cl and C–H···Cl hydrogen bonding and N···Cl pnictogen bonding interactions reported by Hillebrecht [ 148 ] are slightly different to those reported by Yang and coworkers [ 109 ]. Nevertheless, the overall nature of the local topology of non-covalent interactions is very such similar.…”

Section: Illustrative Crystal Systemscontrasting

confidence: 76%

“…Mei et al [ 144 ] were probably the first to show that the protonated 5-amino valeric acid cation, HOOC(CH 2 ) 4 NH 3 + , (5-AVA), can be used as an organic additive for the development of long-term stability of 2D perovskite solar cells. The cation has the advantage that it is not as toxic as organic diammonium cations, which are potentially deleterious to human health [ 109 ]. Subsequently, many such systems were reported, including, for instance, the quaternary representative 5-AVA 2 MA n –1 Pb n Br 3 n –1 series of 2D bromide perovskite compounds [ 145 ] where n = 1–3.…”

Section: Illustrative Crystal Systemsmentioning

confidence: 99%

“…It was argued [ 109 ] that the intermolecular hydrogen bonding in AVA 2 PbCl 4 causes a larger cation penetration depth that enables larger structural deformation than that observed in the reference system PDAPbCl 4 (PDA = pentamethylenediammonium). The deformation of the PbCl 6 octahedra leads to ultrabroadband emission in AVA 2 PbCl 4 , which has an enhanced photoluminescence quantum yield (2.83%) compared to PDAPbCl 4 (0.4%).…”

Section: Illustrative Crystal Systemsmentioning

confidence: 99%

“… Mixed polyhedral (inorganic) and ball-and-stick (organic) models of the crystals of ( a ) [(CH 3 (CH 2 ) 15 NH 3 )PbI 4 ] [ 108 ]; ( b ) [C 5 H 12 NO 2 + ] 4 [Pb 2 Cl 8 ] n; [ 109 ]; ( c ) [(H 3 N(CH 2 ) 12 NH 3 )PbI 4 ] [ 110 ]; and ( d ) [(CH 3 (CH 2 ) 8 NH 3 )PbI 4 ] [ 111 ]. Bond lengths and bond angles associated with selected intermolecular interactions are in Å and degrees, respectively.…”

Section: Figures Schemes and Tablesmentioning

confidence: 99%

“…( c , d ) The crystal structure of [HOOC(CH 2 ) 4 NH 3 ] 2 PbCl 4 (CSD refs. VUHVIG02 [ 109 ] and VUHVIG [ 148 ]) showing the nature of N–H···Cl and C–H···Cl hydrogen bonding and N···Cl pnictogen bonding interactions formed at the organic and inorganic interface. Selected bond distances and bond angles are in Å and degrees, respectively.…”

Section: Figures Schemes and Tablesmentioning

confidence: 99%

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The Pnictogen Bond, Together with Other Non-Covalent Interactions, in the Rational Design of One-, Two- and Three-Dimensional Organic-Inorganic Hybrid Metal Halide Perovskite Semiconducting Materials, and Beyond

Varadwaj

Marques

et al. 2022

IJMS

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The pnictogen bond, a somewhat overlooked supramolecular chemical synthon known since the middle of the last century, is one of the promising types of non-covalent interactions yet to be fully understood by recognizing and exploiting its properties for the rational design of novel functional materials. Its bonding modes, energy profiles, vibrational structures and charge density topologies, among others, have yet to be comprehensively delineated, both theoretically and experimentally. In this overview, attention is largely centered on the nature of nitrogen-centered pnictogen bonds found in organic-inorganic hybrid metal halide perovskites and closely related structures deposited in the Cambridge Structural Database (CSD) and the Inorganic Chemistry Structural Database (ICSD). Focusing on well-characterized structures, it is shown that it is not merely charge-assisted hydrogen bonds that stabilize the inorganic frameworks, as widely assumed and well-documented, but simultaneously nitrogen-centered pnictogen bonding, and, depending on the atomic constituents of the organic cation, other non-covalent interactions such as halogen bonding and/or tetrel bonding, are also contributors to the stabilizing of a variety of materials in the solid state. We have shown that competition between pnictogen bonding and other interactions plays an important role in determining the tilting of the MX6 (X = a halogen) octahedra of metal halide perovskites in one, two and three-dimensions. The pnictogen interactions are identified to be directional even in zero-dimensional crystals, a structural feature in many engineered ordered materials; hence an interplay between them and other non-covalent interactions drives the structure and the functional properties of perovskite materials and enabling their application in, for example, photovoltaics and optoelectronics. We have demonstrated that nitrogen in ammonium and its derivatives in many chemical systems acts as a pnictogen bond donor and contributes to conferring stability, and hence functionality, to crystalline perovskite systems. The significance of these non-covalent interactions should not be overlooked, especially when the focus is centered on the rationale design and discovery of such highly-valued materials.

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Section: Illustrative Crystal Systemscontrasting

confidence: 76%