Molecular and Supramolecular Structures of Triiodides and Polyiodobismuthates of Phenylenediammonium and Its N,N-dimethyl Derivative.

Tatiana A Shestimerova,Alexey B Tarasov,Evgeny V Dikarev,Andrei V Mironov,Andrei V Shevelkov,Mikhail A Bykov,Nikita A Golubev,Zheng Wei,Sergey A Fateev,Ivan Turkevych

doi:10.3390/molecules26185712

Abstract

Despite remarkable progress in photoconversion efficiency, the toxicity of lead-based hybrid perovskites remains an important issue hindering their applications in consumer optoelectronic devices, such as solar cells, LED displays, and photodetectors. For that reason, lead-free metal halide complexes have attracted great attention as alternative optoelectronic materials. In this work, we demonstrate that reactions of two aromatic diamines with iodine in hydroiodic acid produced phenylenediammonium (PDA) and N,N-dimethyl-phenylenediammonium (DMPDA) triiodides, PDA(I3)2⋅2H2O and DMPDA(I3)I, respectively. If the source of bismuth was added, they were converted into previously reported PDA(BiI4)2⋅I2 and new (DMPDA)2(BiI6)(I3)⋅2H2O, having band gaps of 1.45 and 1.7 eV, respectively, which are in the optimal range for efficient solar light absorbers. All four compounds presented organic–inorganic hybrids, whose supramolecular structures were based on a variety of intermolecular forces, including (N)H⋅⋅⋅I and (N)H⋅⋅⋅O hydrogen bonds as well as I⋅⋅⋅I secondary and weak interactions. Details of their molecular and supramolecular structures are discussed based on single-crystal X-ray diffraction data, thermal analysis, and Raman and optical spectroscopy.

Highlights

Polyiodides have recently reemerged as attentively studied compounds, as they can provide reaction media for the fabrication of absorber layers for hybrid perovskite solar cells [1,2]
The polyiodide-assisted fabrication method is capable of transforming a layer of metallic lead several tens of nanometers thick into a uniform layer of a hybrid perovskite by applying triiodide of the selected organic and/or inorganic cation [3,4]
We present new triiodides of rigid organic dications: phenylenediammonium (PDA) and its N,N-dimethyl derivatives (DMPDA), PDA(I3 )2 ·2H2 O (1) and DMPDA(I3 )I (2), respectively

Summary

Introduction

Polyiodides have recently reemerged as attentively studied compounds, as they can provide reaction media for the fabrication of absorber layers for hybrid perovskite solar cells [1,2]. The desire to create efficient synthetic pathways for production of hybrid perovskites is a strong motivation for finding alternatives to solvent-assisted fabrication methods, which exhibit various drawbacks such as inaccurate coverage of the perovskite layer across the substrate. The polyiodide-assisted fabrication method is capable of transforming a layer of metallic lead several tens of nanometers thick into a uniform layer of a hybrid perovskite by applying triiodide of the selected organic and/or inorganic cation [3,4]. Pb-based hybrid perovskites retain their advantages for solar power stations located in non-residential areas, the neurotoxicity of lead should be considered extremely seriously when building integrated perovskite PV systems. It has been demonstrated that among multifarious halometallates, there exists a smaller family of polyhalometallates

Methods

Results

Conclusion