A series of permanently porous luminescent lanthanide frameworks of the general formula, [Na 6 (H 2 O) 6 ]-[Ln(L) 4 ](H 2 O) n Cl, Ln ) Sm (1), Eu (2), Gd (3), Tb (4), and Dy (5), have been prepared by the reaction of trivalent lanthanide salts with sodium-4,4′-disulfo-2,2′-bipyridine-N,N′-dioxide, L. The structures are formed via the one-pot self-assembly of the anionic cubic metalloligand, [Ln(L) 4 ] 5-, and subsequent cross-linking with sodium cations and chloride to afford a three-dimensional network with two-dimensional channels. The cross-linking units involve [Na 4 Cl] 3+ clusters which resemble ideal faces of the halite structure. Both coordinated and uncoordinated water molecules, up to ∼80%, can be reversibly removed from 1-5 as identified using thermal gravimetric analysis/differential scanning calorimetry (TGA/DSC) leaving a rigid and porous framework with a Dubinin-Radushkevich (DR) surface area of 426 m 2 /g determined using CO 2 adsorption. The permanent microporosity of the framework is also supported by the energy level splitting in the luminescence spectra which are maintained in both the hydrated and mostly dehydrated frameworks. Compounds 1-5 were each characterized by X-ray crystallography, TGA/ DSC, water and CO 2 sorption analyses, and luminescence spectroscopy.

The generation of new metal complexes with potentially interesting properties provides the motivation for designing novel polydentate bridging ligands. Herein we report the syntheses of tertiary indolylphenylphosphines L, where L ) diphenyl(3-methyl-2-indolyl)phosphine (P(C 6 H 5 ) 2 (C 9 H 8 N), 1), phenylbis(3-methyl-2-indolyl)phosphine (P(C 6 H 5 )(C 9 H 8 N) 2 , 2), and bis(1H-3-indolyl)methane-(2,12)-phenylphosphine (P(C 6 H 5 )(C 17 H 12 N 2 ), 3). Ligands 1-3 were functionalized at the indolyl nitrogen with a variety of both electron-withdrawing and electron-donating groups. The solid-state structures of 1, 2, and N-functionalized indolylphosphines diphenyl(3-methyl-1-benzyl-2-indolyl)phosphine (P(C 6 H 5 ) 2 (C 9 H 7 N(CH 2 C 6 H 5 )), N-Bz-1) and bis[1-(CH 2 C 6 F 5 )-3-indolyl]methane-(2,12)-phenylphosphine (P(C 6 H 5 )(C 17 H 10 N 2 [CH 2 C 6 F 5 ] 2 ), (N-F 5 Bz) 2 -3), are reported. The reaction of ligands 1-3 with 1 equiv of Pd(COD)Cl 2 led to the formation of Pd(II) complexes of the type [Pd(L)Cl(µ-Cl)] 2 (4, L ) 1; 5, L ) 2; 6, L ) 3). The products were characterized by 1 H, 13 C, and 31 P NMR spectroscopy, mass spectrometry, and elemental analysis. X-ray crystallography established the dimeric structure of the products and confirmed the ability of the ligands to serve, in the absence of base, as monodentate P-donors in reaction with a transition metal. The indolyl NH groups of the complexes 4-6 demonstrate a marked propensity for hydrogen bonding in the solid state.

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A C3-symmetric phosphine with indolyl substituents has been synthesized that demonstrates the capability to bind anions through the indole NH sites and coordinate metal centres through the phosphorus centre.

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