A selenophene-containing conjugated organic ligand for two-dimensional halide perovskites

Abstract

A selenophene-containing conjugated organic ligand 2-(4'-methyl-5'-(5-(3-methylthiophen-2-yl)selenophen-2-yl)-[2,2'-bithiophen]-5-yl)ethan-1-aminium (STm) is synthesized and incorporated into Sn(II)-based two-dimensional perovskites, (STm)2SnI4. By introducing the STm ligand, the band offset between perovskite and ligand can be...

Emerging Two-Dimensional Organic Semiconductor-Incorporated Perovskites─A Fascinating Family of Hybrid Electronic Materials

“…40 Changing the central thiophene to selenophene (4-4, STm) is also synthetically feasible while the properties remain similar. 33 Adding ethyl side chains or increasing the number of methyl groups (4-6, 4Te; 4-7, 4Tdm) modulated the solubility and the lattice strain of OSiPs, which brought a macroscopic variation of surface morphology in 2D/3D perovskite heterostructures. 59 Halide functionalization (4-8, F4Tm; 4-9, Cl4Tm; 4-10, Br4Tm) was achieved on the terminal thiophenes via halogenation, allowing a fine-tuning of energy levels.…”

“…The check marks represent ligands that have confirmed 2D perovskite single-crystal structures. Two rings: 2 - 1 , 2-([2,2′-bithiophen]-5-yl)­ethan-1-aminium (2T); 2 - 2 , 2,2′-([2,2′-bithiophene]-5,5′-diyl)­bis(ethan-1-aminium) (AE2T); 2 - 3 , 2,2′-([2,2′-bithiophene]-5,5′-diyl­bis­(sulfanediyl))­bis(ethan-1-aminium); 2 - 4 , [2,2′-bithiophene]-5,5′-diyl­dimethan­aminium (BThDMA); 2 - 5 , thieno­[3,2- b ]thiophen-2-yl­methan­aminium; 2 - 6 , naphthalen-1-yl­methan­aminium (NMA); , 2 - 7 , 2-(naphthalen-1-yloxy)­ethan-1-aminium; 2 - 8 , naphthalen-2-yl­methan­aminium (NMA); 2 - 9 , 2-(naphthalen-2-yl)­ethan-1-aminium (NEA); 2 - 10 , [1,1′-biphenyl]-4-yl­methan­aminium (BMPA); 2 - 11 , [1,1′-biphenyl]-4,4′-diyl­dimethan­aminium (PP), 2 - 12 , (2-fluoro-[1,1′-biphenyl]-4,4′-diyl)­dimethan­aminium (FPP); 2 - 13 , (5-(4-(ammonio­methyl)-2-fluoro­phenyl)­thiophen-2-yl)­methan­aminium (FPT); 2 - 14 , ( E )-2-(4-styryl­phenyl)­ethan-1-aminium (SA); 2 - 15 , ( E )-2-(4-(3-fluoro­styryl)­phenyl)­ethan-1-aminium (FSA); 2 - 16 , ( E )-2-(4-(phenyl­diazenyl)­phenyl)­ethan-1-aminium. , Three rings: 3 - 1 , 2-([2,2′:5′,2″-terthiophen]-5-yl)­ethan-1-aminium (3T); 3 - 2 , 2,2′-([2,2′:5′,2″-terthiophene]-5,5″-diyl)­bis(ethan-1-aminium) (AE3T); 3 - 3 , 2-(5-(2,2′-dimethyl-[1,1′-biphenyl]-4-yl)­thiophen-2-yl)­ethan-1-aminium (PPT); 3 - 4 , 2-(5-(3′,5′-dimethyl-[1,1′-biphenyl]-4-yl)­thiophen-2-yl)ethan-1-aminium (PPT′); 3 - 5 , 3-(9 H -carbazol-9-yl)propan-1-aminium; 3 - 6 , 3-(1,3-dioxo-1,3,3a,9a-tetrahydro-2 H -benzo­[ f ]­isoindol-2-yl)­propan-1-aminium (NAA); 3 - 7 , 3-(1,3-dioxo-1 H -benzo­[ de ]­isoquinolin-2(3 H )-yl)­propan-1-aminium (NIA); 3 - 8 , anthracen-9-yl­methan­aminium; 3 - 9 , thieno­[3,2- b ]­thiophene-2-phenyl­methyl­ammonium (TTPhMA); Four rings and above: 4 - 1 , 2-([2,2′:5′,2″:5″,2‴-quater­thiophen]-5-yl)­ethan-1-aminium (4T); 4 - 2 , 2-(3‴,4′-dimethyl-[2,2′:5′,2″:5″,2‴-quater­thiophen]-5-yl)­ethan-1-aminium (4Tm); 4 - 3 , 2-(4′-methyl-5′-(7-(3-methyl­thio­phen-2-yl)­benzo­[ c ][1,2,5­]thia­diazol-4-yl)-[2,2′-bithio­phen]-5-yl)­ethan-1-aminium (BTm); , 4 - 4 , 2-(4′-methyl-5′-(5-(3-methyl­thio­phen-2-yl)­seleno­phen-2-yl)-[2,2′-bithiophen]-5-yl)­ethan-1-aminium (STm); 4 - 5 , 2-(3″,4″-dicyano-3‴,4′-dimethyl-[2,2′:5′,2″:5″,2‴-quater­thiophen]-5-yl)­ethan-1-aminium (4TCNm); 4 - 6 , 2-(3‴,4′-diethyl-[2,2′:5′,2″:5″,2‴-quater­thiophen]-5-yl)­ethan-1-aminium (4Te); 4 - 7 , 2-(3′,3‴,4′,4‴-tetra­methyl-[2,2′:5′,2″:5″,2-quater­thiophen]-5-yl)­ethan-1-aminium (4Tdm); 4 - 8 , 2-(5‴-fluoro-3‴,4′-dimethyl-[2,2′:5′,2″:5″,2‴-quater­thio­phen]-5-yl)ethan-1-aminium (F4Tm); 4 - 9 , 2-(5‴-chloro-3‴,4′-dimethyl-[2,2′:5′,2″:5″,2‴-quater­thio­phen]-5-yl)­ethan-1-aminium (Cl4Tm);…”

“…Replacing the central thiophene with thieno­thiophene or dithieno­thiophene imparted the new ligands TT ( 4 - 11 ) or DTT ( 4 - 12 ) to become highly planar structures, which allows a variety of intermolecular interactions, facilitating the nucleation kinetics . Changing the central thiophene to seleno­phene ( 4 - 4 , STm) is also synthetically feasible while the properties remain similar . Adding ethyl side chains or increasing the number of methyl groups ( 4 - 6 , 4Te; 4 - 7 , 4Tdm) modulated the solubility and the lattice strain of OSiPs, which brought a macroscopic variation of surface morphology in 2D/3D perovskite heterostructures .…”

“…The solid-state polymerization reaction under γ-ray was confirmed by the occurrence of a new π–π* transition from UV–vis spectra. Despite OSiPs having a history of over 20 years, few dedicated efforts were made in this field before the burst of perovskite photovoltaics. − With a deep understanding of organic semiconducting materials and the importance of functional organic cations in hybrid 2D perovskite structures, in 2019 our group designed and synthesized a series of new thiophene-based monovalent ligands that form single-crystalline RP-phase OSiPs, establishing OSiPs as a new sub-class of hybrid halide perovskite materials featuring organic semiconducting ligands. − Moreover, our group further extended the scope by designing more functional conjugated ligands, which were successfully incorporated into the 2D halide perovskite framework and were demonstrated to have excellent performance in a variety of electronic and optoelectronic devices. − …”

Stable deep-blue FAPbBr3 quantum dots facilitated by amorphous metal halide matrices

“…15 Although ligands having strong affinity, functional groups can passivate vacancies and reduce ligand shedding, the dynamic adsorption and desorption process of ligands is a key factor to degrade the optoelectronic properties of LHP in the long term. [16][17][18][19][20] According to the properties of common quantum dots (QDs), the core-shell structure can stabilize the core from both chemical and physical factors. 21 Whereas, such a compact core-shell structure can hardly be achieved for LHP due to the incompatibility of the ionic LHP core and covalent shell (ZnS, PbS, etc.).…”