摘要： Electron transfer (ET) in donor-bridge-acceptor (DBA) compounds depends strongly on the structural and electronic properties of the bridge. Among the bridges that support donor - acceptor conjugation, alkyne bridges have attractive and unique properties: they are compact, possess linear structure permitting access to high symmetry DBA structures, and allow torsional motion of D and A, especially for longer bridges. We report conformation dependent electron transfer dynamics in a set of novel DBA compounds featuring butadiyne (C4) bridge, N-isopropyl-1,8-napthalimide (NAP) acceptors, and donors that span a range of reduction potentials (trimethyl silane (Si-C4-NAP), phenyl (Ph-C4-NAP), and dimethyl aniline (D-C4-NAP)). Transient mid-IR absorption spectra of the C≡C bridge stretching modes, transient spectra in the visible range and TD-DFT calculations were used to decipher the ET mechanisms. We found that the electronic excited state energies and, especially, the transition dipoles (S0→Sn) depend strongly on the dihedral angle (θ) between D and A and the frontier orbital symmetry, offering an opportunity to photo-select particular excited states with specific ranges of dihedral angles by exciting at chosen wavelengths. For example, excitation of D-C4-NAP at 400 nm predominantly prepares an S1 excited state in the planar conformations (θ ~ 0) but selects an S2 state with θ ~ 90o, indicating the dominant role of the molecular symmetry in the photophysics. Moreover, the symmetry of the frontier orbitals of such DBA compounds not only defines the photo-selection outcome, but also determines the rate of the S2→S1 charge separation reaction. Unprecedented variation of the S2-S1 electronic coupling with θ by over four orders of magnitude results in slow ET at θ ca. 0o and 90o but extremely fast ET at θ of 20-60o. The unique features of high-symmetry alkyne bridged DBA structures enable frequency dependent ET rate selection and make this family of compounds promising targets for the vibrational excitation control of ET kinetics.