The design and synthesis of organic and hybrid molecular networks in the crystalline state has been investigated using iterative self-assembly processes involving preprogrammed complementary molecular building blocks called tectons. This approach is based on molecular recognition events between dicationic hydrogen bond donors and anionic hydrogen bond acceptors tectons. Thus, the combination of intrinsically luminescent molecular tectons belonging to the family of cationic bis-benzimidazoliums with polycyanometallates anions leads to the formation of luminescent hybrid molecular networks in the crystalline state. Their optical properties have been studied in the solid state. Similarly, the association of bis-amidiniums, dicationic bricks, to azodibenzoates type anions leads to crystalline assemblies presenting photo-switching property, i.e. the ability to isomerise under light stimulus.
