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Di(p-methoxyphenyl)amine end-capped tri(p-thiophenylphenyl)amine based molecular glassed as hole transporting materials for solid-state dye-

sensitized solar cellsThanh-Tuân Bui,a* Said Karim Shah,b,c Xavier Sallenave,a Mamatimin Abbas,b Gjergji Sini,a

Lionel Hirsch,b* and Fabrice Goubarda*

aLaboratoire de Physicochimie des Polymères et des Interfaces (LPPI), Université de Cergy-

Pontoise, 5 mail Gay Lussac, Neuville-sur-Oise, 95031 Cergy-Pontoise Cedex, France. bUniv. Bordeaux, IMS, UMR 5218, F-33607 Pessac, France and CNRS, IMS, UMR 5218, F-

33607 Pessac, France.cDepartment of Physics, Abdul Wali Khan University Mardan, Khyber Pakhtunkhwa, 23200

Pakistan.

*Corresponding authors: tbui@u-cergy.fr (T.-T. B.); lionel.hirsch@ims-bordeaux.fr (L. H.);

fabrice.goubard@u-cergy.fr (F. G.);

Supplementary material

Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2015

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Figure S1. TGA (A) and 2nd heating cycle DSC (B) curves of compounds 1-3 (– 1, – 2, – 3) under argon. Heating rate: 20°C/min

Figure S2. CV of 1-3 (– 1, – 2, – 3) recorded in 0.1 M TBAClO4/THF. Scan rate: 100 mV/s, working electrode: Pt disc

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Figure S3. (a) Theoretical absorption spectra of compounds 1-3 obtained at the TD-B3LYP/6-31G(d,p) level in gas phase. (b) Theoretical absorption spectra of compound 1, indicating the nature of the low energy band. (c) pictograms of orbitals involved in the transitions corresponding to the low-energy absorption band.

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Figure S4. (a) -LUMO pictograms of compounds 1-3 in their cationic state (corresponding to HOMO in the nomenclature of the neutral compounds). Note the absence of contribution of the DPA blocks to this orbital. (b) Lateral view of the optimized structure of compound 1. Note that the steric hindrance between the DPA groups on adjacent molecules is expected to prevent from the establishement of an efficient short-distance overlap of TPA-Th backbones. (c) Lateral and (d) top “Artist” views of a (non-optimized) dimer containing two molecules of compound 1 (one of them is highlighted in yellow for easier distinction).

The negligible contribution of the DPA groups to the HOMO of compounds 1-3 (Figure a) is expected to prevent from efficient HOMO-HOMO overlap in the case of DPA….DPA interaction between adjacent molecules. A similar effect is to be expected in the case of interaction between the TPA-Th moieties of adjacent molecules, due to the steric hindrance induced by the DPA groups (Figures d and e).