Table 1.

Measured and Computed HFI and NQI Parameters of ¹⁴N Atoms Coupled to Superoxidized MnCat and Relevant Model Complexes

Species	assign.a	Aiso (MHz)	e2Qq/h (MHz)	η	Ref.
LP	N1	2.88	2.19	0.58	14
LP + N3−		3.34	1.97	0.74
LP + CN−		3.86	1.93	0.74
LPmod1	N1	+1.98	−2.40	0.71	28
	N2	−3.27	−2.44	0.70
LPmod2	N1	+2.08	−2.40	0.70
	N2	−4.04	−2.38	0.72
LPmod3	N1	+3.30	+1.98	0.89
	N2	−6.62	+2.02	0.93
LPmod4	N1	−1.56	+2.02	0.91
	N2	+4.73	+1.90	0.49
LP	N1	+2.67	2.25	0.58	this study
	N2	−5.75	2.01	0.79
TT	N1	2.3	2.44	0.44	79
TT	N1	2.45	2.34	0.51	13
methylated TT		>4
TT	N1	+2.28	2.29	0.50	this study
	N2	−5.2	2.25	0.65
CYCLAMb		2.70	3.06	0.39	80
	Mn(III)ax	9.23	2.98		71
TMPAc	Mn(III)ax	11.20	3.02		71
BIPYd	Mn(III)ax	9.4	2.9		17
	Mn(III)ax	11.4	3.0		81
	Mn(III)ax	11.3			63
		2.78	2.42	0.14	80
PHENe		2.80	2.38	0.13	80
	Mn(III)ax	11.54	3.13		63
TACNf		2.73	3.06	0.36	80
BISPICENg		2.51	2.87	0.54	80
	Mn(III)ax	12.1	2.3		63
BPEAh		3.04	2.86	0.20	80
TPENi		2.51	2.73	0.15	80
DTNEj	Mn(III)ax	+12.0			72
	Mn(III)eq	−1.9
	Mn(IV)ax	+1.9
	Mn(IV)eq	+1.5			45
PSII	H332	7.3	1.98	0.84

^aDesignations “ax” and “eq” refer to nitrogen coordination to a pseudo-octahedral metal ion in the axial and equatorial positions, respectively. For example, the designation “Mn(III)ax” refers to a nitrogen ligand bound along the local z-axis of a Mn(III) ion.

^bCYCLAM = 1,4,8,11-tetraazacyclotetradecane

^cTMPA = tris(2-methylpyridyl)amine

^dBIPY = 2,2′-bipyridine

^ePHEN = 1,10-phenanthroline

^fTACN = 1,4,7-triazacyclononane

^gBISPICEN = N,N′-bis(2-pyridylmethyl)ethane-1,2-diamine

^hBPEA = N,N-bis(2-pyridylmethyl)ethaneamine

ⁱTPEN = N,N,N′,N′-tetrakis(2-pyridylmethyl)-1,2-ethanediamine

^jDTNE = 1,2-bis(1,4,7-triazacyclonon-1-yl)ethane). These HFI were computed using the B3LYP hybrid density functional.