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We report solid-state 13C NMR spectra of urea-loaded copper benzoate, Cu 2 (C 6 H 5 CO 2) 4 ·2(urea), a simplified model for copper paddlewheel-based metal-organic frameworks (MOFs), along with first-principles density functional theory (DFT) computation of the paramagnetic NMR (pNMR) chemical shifts. Assuming a Boltzmann distribution between a diamagnetic open-shell singlet ground state (in a broken-symmetry Kohn-Sham DFT description) and an excited triplet state, the observed δ (13C) values are reproduced reasonably well at the PBE0-⅓/IGLO-II//PBE0-D3/AE1 level. Using the proposed assignments of the signals, the mean absolute deviation between computed and observed 13C chemical shifts is below 30 ppm over a range of more than 1100 ppm. Image 1 • Cu(C 6 H 5 CO 2) 4 ·2(urea), a model for metal-organic frameworks, shows pNMR shifts for 13C. • The shifts stem from a triplet state in equilibrium with the singlet ground state. • Shifts are computed assuming a Boltzmann distribution of the two spin states. • Sign and magnitude of the pNMR shifts can be rationalised by the triplet spin density. [ABSTRACT FROM AUTHOR]