. Author manuscript; available in PMC: 2021 Dec 17.

Published in final edited form as: J Phys Chem B. 2020 Dec 3;124(50):11357–11370. doi: 10.1021/acs.jpcb.0c08201

Table 1.

Hyperfine Coupling Constants (HFCC) and g-values of radicals reported in this work

Compound/Type/ Radical	Hyperfine couplings (G)			g-value (exp)
Compound/Type/ Radical	Site(nucleus)	Exp	Theory	g-value (exp)
π/T(5′-CH₂)-NH• ^a (5′-AZT)	β-protons, (H5′, H5″)	Sum 91^a		g_‖ = 2.0020^a, g_⊥=2.0043^a
	N5′-H (α-proton)	(-, -, −30)^a	(−39.8, 0.4, −26.7)^a
	N5′-coupling	(0, 0, 43)^a	(0, 0, 41.8) G ^a
π /U-5-CH₂-NH• ^b (AmdU) 5/π/dU-5′-CH₂-NH•	β-protons, (H5, H5)^b β-protons, (H5′, H5″) (for 5)	Sum 93.5^b Sum 90.5	----------------------	g_‖ = 2.0020, g_⊥=2.0043
	N5-H (α-proton) ^b N5′-H (α-proton)	(-, -, −30)^a
	N5/N5′-coupling	(0, 0, 42.5)
α-azidoalkyl radical5/π/dU-5′-CH•-N₃	1αH 1αH 1N	-------------	(−10.97, −15.03,−5.09) (−14.46,−20.64,−6.67) (10.5, −0.5, −1.32)^c	2.0038 yy 2.0021 zz 2.0043 xx
σ U-5-CH=N• ^b	β-proton, (H5) ^b N5-coupling ^b	82 ^b (0, 0, 36.5) ^b	(71.8, 78.0,72.8) (−4.2, 0, 37.7)^b	g_‖ = 2.0016, g_⊥=2.0040
5 σ dR-5′-CH=N•	β-proton, (H5′) 5 N5′-coupling	82 (0, 0, 36.5)	(72.9, 78.7, 73.0)^d (−4.44, −0.9, 36.6)^d	g_‖ = 2.0016, g_⊥=2.0040
1 π dC(C2′)-ND• (π C(C2′)-ND•) 2 π dU(C2′)-ND• (π U(C2′)-ND•)	N2′-coupling	(0, 0, 40.5)	--------------------------	g_‖=2.0020, g_⊥=2.0043
	C2′-H (β-proton)	51.5
	N2′-H (α-proton)	(,,−28) ^e
3 π 2′,3′-ddU(C3′)-ND•	N3′-coupling	(0, 0, 37.5) ^e	-------------------------	g_‖=2.0020, g_⊥=2.0043
	C3′-H (β-proton)	41 ^e
	N3′-H (α-proton)	(,,−28) ^e
4 π C(C4′)-ND•	N4′-coupling	(0, 0, 37.5) ^e	--------	g_‖=2.0020, g_⊥=2.0043
4 π C(C4′)-ND•	N4′-H (α-proton)	(,,−28) ^e	--------	g_‖=2.0020, g_⊥=2.0043

Taken from reference 8.

Taken from reference 7.

Employing B3LYP/6-31G** method, structure of 5′-CH•-N₃ was optimized and HFCCs of the fully optimized structure of 5′-CH•-N₃ was calculated (see SI). Linewidth = 3.5 G, and a mixed line shape (Lorentzian/Gaussian =1) was employed to simulate the experimental spectrum.

Employing B3LYP/6-31G** method, structures of 5′-CH=N• of U-5-CH=N• were fully optimized and HFCCs of these optimized structures were calculated (see SI). Linewidths as (7, 5, 5) G and line shape with a mixed Lorentzian/Gaussian = 1 were employed to simulate the experimental spectrum.

Taken from reference 8. For simulation, we used linewidth as 10 G, and line shape with a mixed Lorentzian/Gaussian = 1.