Synthesis, characterization, and polymerization of new ferrocene-fluorene complexes. A novel high-molecular-weight conjugated polymer with pendant ferrocene groups

Functionalization of 9‐(Dicyanomethylene)fluorene Derivatives with Substituted Acetylenes

“…One remarkable feature in this study is the observation of a solvatochromic phenomenon for the lowest-energy MLCT band in 4 (hexane Ǟ CH 2 Cl 2 , red shift of 30 nm), consistent with a dipolar excited state due to intramolecular charge-transfer (ICT) transition from the electron-donating ferrocenyl group to the electron-withdrawing cyano group through the conjugated system. [14] (1)ϪC (18) 2.019 (6) Fe (1)ϪC (19) 2.039(6) Fe (1)ϪC (20) 2.051 (6) Fe (1)ϪC (21) 2.051(6) Fe(1)ϪC (22) 2.030 (6) Fe (1)ϪC (23) 2.046(8) Fe (1)ϪC (24) 2.034 (7) Fe (1)ϪC (25) 2.034(7) Fe (1)ϪC (26) 2.045 (8) Fe (1)ϪC (27) 2.025(7) C (13)ϪC (14)ϪC (15) 122.4(5) 121.9(5) C (14)ϪC (15)ϪN (1) 176.8 (7) 174.6(7) C (14)ϪC (16)ϪC (17) 176.9(6) 176.4 (7) C (16)ϪC (17)ϪC (18) 175.0(6) 173.9(7) (21)ϪC (22) 1.360(3) C (22)ϪC (23) 1.429(3) C(23)ϪN (1) 1.139(3) C (22)ϪC (24) 1.436(3) C (24)ϪN (2) 1.143(3) C(25)ϪC (26) 1.194(3) C(7)ϪC(8)ϪC (9) 175.6(2) C (21)ϪC …”

“…[12] Compound 4 is structurally similar to 3, except that a ferrocenylacetylene group is bound to the methylene carbon atom at C (14) instead. To the best of our knowledge, compounds 3 and 4 represent the first structurally characterized examples of fluorene derivatives possessing σ-acetylene groups at their 9-methylene positions.…”

“…The exo double bond C (13)ϪC (14) is distorted from planarity by 6°[defined by C(1)ϪC (13)ϪC (14)ϪC (15)] in 3, but the distortion is less pronounced in 4. The C (13)ϪC (14) double bond length is typical at 1.361(8) (3) (6), [14] 2,7-diformyl-9-fluorenyl:…”

“…1.340(3), [14] 2,7-diethynyl-9-fluorenyl: 1.348(3) Å ], [9c] trans-[Ph(Et 3 P) 2 PtCϵCArCϵCPt(PEt 3 ) 2 Ph] [Ar ϭ 9-(ferrocenylmethylene)fluorene-2,7-diyl: 1.37(2), [9c] 9-(dicyanomethylene)fluorene-2,7-diyl: 1.348(9) Å ], [9b] 9-[cyano(dimethylamino)methylene]-2,4,5,7-tetranitrofluorene [1.388(4) Å ] [8e] and other polynitro-substituted 9-(dicyanomethylene)fluorenes.…”

“…We anticipate that conjugation through the molecule in the ground-state configuration should produce a shortening of the C(6)ϪC (7), C(8)ϪC(9), C (18)ϪC (25), and C(26)ϪC(27) bonds [1.425(2)Ϫ1.434(2) Å ] and a lengthening of the C(7)ϪC(8) and C(25)ϪC(26) bonds. [14] Again, no plane-to-plane stacking between adjacent molecules occurs in the crystal lattice of 8.…”