The complexation of the macrocyclic cavitand cucurbit[7]uril (Q7) with a series of amino acids (AA) with different side chains (Asp, Asn, Gln, Ser, Ala, Val, and Ile) is investigated by ESI-MS techniques. The 1:1 [Q7 + AA + 2H]²⁺ adducts are observed as the base peak when equimolar Q7:AA solutions are electrosprayed, whereas the 1:2 [Q7 + 2AA + 2H]²⁺ dications are dominant when an excess of the amino acid is used. A combination of ion mobility mass spectrometry (IM-MS) and DFT calculations of the 1:1 [Q7 + AA + 2H]²⁺ (AA = Tyr, Val, and Ser) adducts is also reported and proven to be unsuccessful at discriminating between exclusion or inclusion-type conformations in the gas phase. Collision induced dissociation (CID) revealed that the preferred dissociation pathways of the 1:1 [Q7 + AA + 2H]²⁺ dications are strongly influenced by the identity of the amino acid side chain, whereas ion molecule reactions towards N-butylmethylamine displayed a common reactivity pattern comprising AA displacement. Special emphasis is given on the differences between the gas-phase behavior of the supramolecular adducts with amino acids (AA = Asp, Asn, Gln, Ser, Ala, Val, and Ile) and those featuring basic (Lys and Arg) and aromatic (Tyr and Phe) side chains.

Chemical modification of the trinuclear [Mo₃(μ₃-S)(μ₂-S₂)₃Br₆]²⁻ cluster, at either the outer bromine or the disulfide ligands, allows the facile preparation of the dianions [Mo₃(μ₃-S)(μ₂-S₂)₃(tdas)₃]²⁻ ([1]²⁻) (tdas = 1,2,5-thiadiazole-3,4-dithiol), [Mo₃(μ₃-S)(μ₂-SSe)₃Br₆]²⁻ ([2]²⁻) and [Mo₃(μ₃-S)(μ₂-S₂)₃Cl₆]²⁻ ([3]²⁻). Electrocrystallization of bis(ethylenedithio)tetrathiafulvalene (ET) in the presence of these dianions affords a series of charge transfer salts, namely (ET_A)(ET_B)[1], (ET_A)(n-Bu₄N)[2], (ET_A)(ET_B)[3]₂·CH₃CN, and ((ET_A)(ET_B)(ET_C)(ET_D))₂{[3]₂Cl}·CH₃CN, where the ET subscripts denote crystallographically independent molecules. In all cases, the various cluster–cluster, cluster–donor and donor–donor interactions give rise to rich structural diversity in the inorganic and organic sublattices. Raman spectroscopy has been used to account for the degree of charge transfer in the organic donor ET. The ET molecules are oxidized to the integral 1+ oxidation state in compounds (ET_A)(ET_B)[1] and (ET)(n-Bu₄N)[2] and to the integral value of 2+ in compound (ET_A)(ET_B)[3]₂·CH₃CN. Their transport properties reveal semiconducting behaviour with a room temperature conductivity of 4 × 10⁻⁵ S· cm⁻¹ and an activation energy of 280 meV for compound (ET_A)(ET_B)[1] while the other two compounds are insulators. Non-integer values less than 1+ are observed for ((ET_A)(ET_B)(ET_C)(ET_D))₂{[3]₂Cl}·CH₃CN which shows metallic behavior at high temperatures with an irreversible transition to an activated conductivity at ca. 270 K.