Table 1. Comparison of the Experimentally Obtained HFCCs Values of C3′• and C2′• in Gauss (G) with Those Obtained by Calculation Using DFT/ωb97x/6-31G(d) Method.

			HFCC (G)
			theory				expa,b
molecule	radical	atoms	AIso	AAniso		A(total)a	A(total)a,b
gemcitabine	C3′• pH ca. 7	two β-F-atoms (C2′)	37.24	Axx	–14.61	22.63	15.0
				Ayy	–13.95	23.29	15.0
				Azz	28.56	65.8	69.0
			69.55		–29.79	39.76	15.0
					–27.76	41.79	15.0
					57.55	127.1	105.0
		β-H-atom (C4′)	28.61		–1.73	26.88	15.0
					–1.03	27.58	15.0
					2.76	31.37	24.0
	C3′• pH ca. 9–12	two β-F-atoms (C2′)					17.0
							17.0
							86.0
		β-H-atom (C4′)					15.0
							15.0
							24.0
MeFdCc	C2′•	three β-H-atoms CH3 group	17.5d (average)				21.5
		one β-H-atom (C1′-H)	23.31		–1.77	21.54	25.5
					–0.73	22.77
					2.51	25.82

^aA_(total) = A_Iso + A_Aniso.

^bExperiments give the magnitude but not the sign of the couplings. Estimated errors are of ±2 G for A_zz and ±4 G for A_xx and also for A_yy. See Supporting Information Figure S3 for details.

^cCalculated in the presence of one water molecule

^dOnly isotropic HFCC values have been considered.