A novel metal-organic framework of Cu(I), {[Cu(bphz)(2)] center dot 2BF(4)}(n) (1) (bphz = 1,2-bis(4-pyridylmethylene)hydrazine) has been synthesized and structurally characterized. Structure determination reveals a 3D diamondoid network with 1D channels filled with the BF4-anions which undergoes F center dot center dot center dot F interactions forming 1D (BF4-)(n) chains in the crystallographic c-axis. The six independent 3D diamondoid networks are sixfold interpenetrating, forming a rare example of sixfold interpenetrated 3D diamondoid network. The framework also exhibits photoluminescence properties and selective reversible anion exchange ability with the NO3- anions, but not with the CIO4- and PF6- anions. The highly selective anion exchange ability is correlated with the size and shape of the anions compare to the channel aperture. (c) 2009 Elsevier B.V. All rights reserved.`