臺灣博碩士論文加值系統

Abstract
Unlike 7-azaindole consisting of the tetrameric configuration, 3-methyl-7-azaindole (3MAI) exists solely as intact double hydrogen-bonded dimeric forms in a single crystal. Both steady state and time-resolved measurements down to 8.0 K reveal remarkable deuterium isotope effects on the rate of excited-state double proton transfer (ESDPT) in the N(1)-deuterated 3MAI (3MAI-d) single crystal. The rates of ESDPT for the 3MAI-d dimer resolved at < 150 K are mainly governed by the proton tunneling mechanism. At < 12 K, the nearly temperature-independent ESDPT dynamics lead us to qualitatively deduce a barrier height of ~ 1.73 kcal/mol for the 3MAI-d dimer. The results provide an ideal model to investigate the intrinsic ESDPT dynamics for 7-azaindole analogues in which the structural information is well documented.
The mechanism of excited-state double proton transfer (ESDPT) reaction of 7-azaindoles in pure water has been solved through design and syntheses of 3-Cyano-7-azaindole (3CAI) and its derivatives. Dual emission consisting of normal (lmax = 350 nm) and tautomer band (lmax = 475 nm) was resolved for 3CAI in pure water. Dynamical studies clearly revealed that the entire rise time of the tautomer emission of 850 ps is identical with the decay time (tf = 855 ps) of the normal emission. Remarkable deuterium isotope effect was observed in D2O where the rise time of 3.50 ns of the tautomer emission correlates well with the lifetime (3.45 ns) of the normal emission. The results lead us to conclude that dynamics of ESDPT with a rate of 850 ps-1 in water (or 3.50 ns-1 in D2O) originate from the entire ground-state solvated species, resolving a long-standing controversy regarding the mechanism of water catalyzed ESDPT in 7-azaindoles.
We have demonstrated a new class of donor-{saturated hydrocarbon bridge}-acceptor (D-B-A) dyads based on a systematic approach to evaluate the corresponding photoinduced electron transfer process. Among these dyads heptacyclo[6.6.0.02,6.03,13.04,11.05,9.010,14]tetradecane (HCTD) was used as a unique spacer, which possesses a geometry of high symmetry (D2d), rigidity and linearity so that electron transfer processes can be examined between donor and acceptor substituents aligned along a straight line across the s-framework. In certain cases, via synthetic routes, the relative orientation of p-orbitals between donor and acceptor was adjusted to either a coplanar (0º) or perpendicular (90º) dihedral angle with respect to each other so that a comparative study could be made by tuning their relative electron coupling properties. The results in combination with theoretical approaches render valuable information on the spectroscopy and dynamics of excited-state electron transfer as functions of donor/acceptor electronic states, orientation as well as solvent properties.

Abstract
Unlike 7-azaindole consisting of the tetrameric configuration, 3-methyl-7-azaindole (3MAI) exists solely as intact double hydrogen-bonded dimeric forms in a single crystal. Both steady state and time-resolved measurements down to 8.0 K reveal remarkable deuterium isotope effects on the rate of excited-state double proton transfer (ESDPT) in the N(1)-deuterated 3MAI (3MAI-d) single crystal. The rates of ESDPT for the 3MAI-d dimer resolved at < 150 K are mainly governed by the proton tunneling mechanism. At < 12 K, the nearly temperature-independent ESDPT dynamics lead us to qualitatively deduce a barrier height of ~ 1.73 kcal/mol for the 3MAI-d dimer. The results provide an ideal model to investigate the intrinsic ESDPT dynamics for 7-azaindole analogues in which the structural information is well documented.
The mechanism of excited-state double proton transfer (ESDPT) reaction of 7-azaindoles in pure water has been solved through design and syntheses of 3-Cyano-7-azaindole (3CAI) and its derivatives. Dual emission consisting of normal (lmax = 350 nm) and tautomer band (lmax = 475 nm) was resolved for 3CAI in pure water. Dynamical studies clearly revealed that the entire rise time of the tautomer emission of 850 ps is identical with the decay time (tf = 855 ps) of the normal emission. Remarkable deuterium isotope effect was observed in D2O where the rise time of 3.50 ns of the tautomer emission correlates well with the lifetime (3.45 ns) of the normal emission. The results lead us to conclude that dynamics of ESDPT with a rate of 850 ps-1 in water (or 3.50 ns-1 in D2O) originate from the entire ground-state solvated species, resolving a long-standing controversy regarding the mechanism of water catalyzed ESDPT in 7-azaindoles.
We have demonstrated a new class of donor-{saturated hydrocarbon bridge}-acceptor (D-B-A) dyads based on a systematic approach to evaluate the corresponding photoinduced electron transfer process. Among these dyads heptacyclo[6.6.0.02,6.03,13.04,11.05,9.010,14]tetradecane (HCTD) was used as a unique spacer, which possesses a geometry of high symmetry (D2d), rigidity and linearity so that electron transfer processes can be examined between donor and acceptor substituents aligned along a straight line across the s-framework. In certain cases, via synthetic routes, the relative orientation of p-orbitals between donor and acceptor was adjusted to either a coplanar (0º) or perpendicular (90º) dihedral angle with respect to each other so that a comparative study could be made by tuning their relative electron coupling properties. The results in combination with theoretical approaches render valuable information on the spectroscopy and dynamics of excited-state electron transfer as functions of donor/acceptor electronic states, orientation as well as solvent properties.

Chapter 1: Introduction ………………………………….…… … 1
Part 1: Dynamics of proton transfer in 7-azaindole host/guest hydrogen-bonded complexes………………………………….…. … 1
I. ESDPT dynamics in the 7AI dimmer………………….…... … 1
II. ESDPT dynamics in 7AI CDHB complexes……………..... … 6
III. Excited-state biprotonic transfer in hydroxylic solvents.... … 7
a.7AIs In alcohols……………………………………… … 7
b.7-Azaindoles in aqueous solution……………………. … 16
Part 2: Electron Transfer － Theoretical Models and Covalently Linked Systems Based on Organic Components………………………… … 18
I. The Superexchange Mechanism…………………………... … 21
References……………………………………………………….. … 24
Chapter 2: Excited-State Double Proton Transfer on 3-Substituted-7-Azaindole Analogues………,…… … 36
Part 1: Excited-State Double Proton Transfer on 3-Methyl-7-Azaindole in a Single Crystal; Deuterium Isotope/Tunneling Effect,…. … 36
1.Results……………………………………………………. … 38
2.Discussion………………………………………………... … 42
3.Conclusion………………………………………….…….. … 47
4.Experimental Section……………………………………. . … 47
References……………………………………………………. … 51
Part 2: Water Catalyzed Excited-State Double Proton Transfer in 3-Cyano-7-Azaindole; The Resolution of the Proton-Transfer Mechanism for 7-Azaindoles in Pure Water…………… … 65
1.Results and Discussion………………………………..….. … 67
2.Conclusion………………………………………………... … 69
3.Experimental Section……………………………………... … 70
References……………………………………………………. … 72
Chapter 3. Photoinduced Electron Transfer Reaction Tuned by Donor-Acceptor Pairs via the Rigid, Linear Spacer Heptacyclo[6.6.0.02,6.03,13.04,11.05,9.010,14]tetradecane.. … 77
1.Results and Discussion……………………….………...… … 79
2.Conclusion………………………………………………... … 92
3.Experimental Section…….……………………………….. … 92
References………………………………………………..…. … 104

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