Stable phospha- and arsaalkenes were used to synthesize polymers containing unsaturated P[double bond, length as m-dash]C and As[double bond, length as m-dash]C moieties. The composition, chemical environment, structure, optical, and electronic properties of the monomers and polymers were elucidated. The incorporation of the heteroatom-carbon double bonded units efficiently perturbs the optoelectronics and solid state features of both monomeric and polymeric scaffolds. Proof-of principle work supports their responsive character through post-functionalisation and electrochromic behaviour. To the best of our knowledge, this is the first example of a polymer containing arsenic-carbon double bonds.
The
substitution of 2,7-dibromo-9-fluorenyl phosphaalkenes with
heteroaromatic substituents (bithiophene, benzothiophene, pyridine)
offers access to interesting push–pull dye molecules. Steric
shielding due to the bulky P-substituent gives marked different reactivities
at the 2- and 7-positions, allowing the synthesis of mixed/asymmetric
derivatives. Further functionalization via gold(I) coordination was
demonstrated and increased the acceptor character, concomitant with
a red-shifted absorption.
A series of silver coordination polymers based on the 9,9′‐bis(4,5‐diazafluorene) (BDF‐H2) ligand is presented. The choice of counterions and reaction conditions dictate the observed topology on the final systems by influencing the silver coordination environment. Coordination modes, flexibility of the ligand and extended π–π stacking interactions have allowed the preparation and crystallographic characterisation of one 1D‐ and three 2D‐coordination polymers: 1D‐[Ag(BDF‐H2)(DMSO)]n(X)n (where X = OTf– and ClO4–); 1D‐[Ag2(BDF‐H2) m1‐(TfO)2,m2‐(TfO)2]n(TfO)n, and 2D‐[Ag2(BDF‐H2)3]n(PF6)2n.
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