DOI: 10.5061/dryad.0rxwdbs7j
title: Design, synthesis and theoretical simulations of novel spiroindane-based enamines as p-type semiconductors

description: The search for novel classes of hole transporting materials (HTMs) is a
 very important task in advancing the commercialization of various
 photovoltaic devices. Meeting specific requirements, such as thermal
 stability, appropriate energy levels, and charge-carrier mobility, is
 essential for determining the suitability of an HTM for a given
 application. In this work, two spirobisindane-based compounds, bearing
 terminating hole transporting enamine units, were strategically designed
 and synthesized using commercially available starting materials. The
 isolated compounds exhibit sufficient thermal stability and are amorphous
 with high glass-transition temperatures (&gt;150⁰C), minimising the
 risk of direct layer crystallization. V1476 stands out with the highest
 zero-field hole-drift mobility, approaching 1×10-5 cm2Vs-1. To assess the
 compatibility of the HOMO energy levels of the spirobisindane-based HTMs
 in solar cells, the solid-state ionization potential (Ip) was measured by
 the electron photoemission in air of the thin-film method. The favourable
 morphological properties, energy levels, and hole mobility in combination
 with a simple synthesis make V1476 and related compounds promising
 materials for HTM applications in antimony-based SCs and
 triple-cation-based perovskite SCs.
description: # Design, synthesis and theoretical simulations of novel spiroindane-based
 enamines as p-type semiconductors
 [https://doi.org/10.5061/dryad.0rxwdbs7j](https://doi.org/10.5061/dryad.0rxwdbs7j) Two novel spirobisindane-based enamines **V1476** and **V1481** were designed and synthesized from commercially available starting materials. Following a comprehensive assessment of their thermal, optical, and photophysical properties, it is evident that these HTMs emerge as promising candidates for applications in organic or hybrid electronics. The synthesized compounds exhibit noteworthy thermal and electrochemical stability, possess suitable energy levels, and demonstrate sufficiently high drift carrier mobility. ####  Datasets included:  1.    **Contact angle measurements.jpg**: Data on measurement of contact angle (θ), which was carried out to assess the hydrophobicity of the synthesized spirobisindane-based enamines **V1476**, **V1481,** and that of spiro-OMeTAD for comparison. (**Figure S3** in "RSOS-232019_Supporting_Information" supplemental document)  2.    **All .cub and .mol files**: Results of quantum chemistry simulations (**Figure S4** in "RSOS-232019_Supporting_Information" supplemental document):  A 3D view of the most stable conformations of **V1476** and **V1481** was obtained using the program GausView 5.0.8. Gaussian files of .gjf type v1476as.gjf, v1481as.gjf, and v1481bs.gjf are presented for visualization of required projections. *Note: later, the .gjf files were converted to MDL type files (.mol) to ensure that they can be viewed with the free molecular editor software Avogadro (see information below).* Molecular orbitals were obtained using the program GausView 5.0.8.  Gaussian files of *.cub type v1476as_X.cub, v1481as_X.cub,  v1481bs_X.cub  are presented for visualization of required projections. For all conformers LUMO+1 corresponds to X=393, LUMO corresponds to X=392, HOMO corresponds to X=391, and HOMO-1 corresponds to X=390. **Nuclear visualization:** v1476as.mol, v1481as.mol,  v1481bs.mol **Nucleus plus molecular orbitals:** v1476as_390.cub, v1476as_391.cub, v1476as_392.cub, v1476as_393.cub\ v1481as_390.cub, v1481as_391.cub, v1481as_392.cub, v1481as_393.cub\ v1481bs_390.cub, v1481bs_391.cub, v1481bs_392.cub, v1481bs_393.cub The following routine is necessary for the usage of GausView: 1st stage (Nuclear visualization only): FILE/Open, File type: - select CUBE files: cub, Select…  Open 2nd stage (Nucleus plus molecular orbitals): Results: Surfaces/Contours, Surface action: New surface, Select MO… Close The files can be viewed using a free open-source cross-platform molecular editor Avogadro ([https://avogadro.cc/).](https://avogadro.cc/\).)