%0 Generic %A Fave, Claire %A Hissler, Muriel %A Kárpáti, Tamás %A Rault-Berthelot, Joëlle %A Deborde, Valérie %A Toupet, Loic %A Nyulászi, László %A Réau, Régis %D 2004 %T Connecting π-Chromophores by σ-P−P Bonds:  New Type of Assemblies Exhibiting σ−π-Conjugation %U https://acs.figshare.com/articles/dataset/Connecting_Chromophores_by_P_P_Bonds_New_Type_of_Assemblies_Exhibiting__Conjugation/3338815 %R 10.1021/ja0317067.s001 %2 https://acs.figshare.com/ndownloader/files/5178031 %K chemical modifications %K band gap %K HOMO %K Theoretical studies %K electroactive materials %K thienyl substituents %K biphosphole %K modifications offer %K P centers %K interaction %K nucleophilic σ 3 %K UV %K assembly %X To study the ability of σ-P−P skeleton to mediate interaction between π-chromophores, 1,1‘-biphospholes bearing phenyl or thienyl substituents at the 2,2‘ and 5,5‘-position have been prepared and studied. These air-stable derivatives are readily available via a “one-pot” synthesis starting from diynes. Theoretical studies and UV−vis data clearly establish that the two π-systems interact via the σ-P−P bridge. This through-bond interaction results in a lowering of the optical HOMO−LUMO gap of the assemblies. The nucleophilic σ3-P centers of these 1,1‘-biphospholes allow chemical modifications of the σ-bridge. These modifications offer further tuning of the optical properties of the assembly. Electrooxidation of the thienyl-substituted 1,1‘-biphosphole results in electroactive materials characterized by low optical band gap and reversible p-doping. %I ACS Publications