The reaction of anhydrous [12]crown-4 with a 1:1 ethanol adduct of the three-mercury anticrown (o-C 6 F 4 Hg) 3 (1) under Ar results in the formation of a double-decker sandwich complex {[(o-C 6 F 4 Hg) 3 ] 2 ([12]crown-4)} ( 4). The molecule of the crown ether in 4 is located between the mutually parallel planes of two mercury macrocycles and is coordinated to each of them through Hg-O secondary interactions. In the crown ether ligand, all four oxygen atoms are involved in the bonding to the molecules of 1, while in each anticrown species only two Hg centers take part in the coordination. If aqueous [12]crown-4 is used in the reaction with 1, the other double-decker sandwich, {[(o-C 6 F 4 Hg) 3 ] 2 ([12]crown-4)(H 2 O) 2 } (5), containing one crown ether molecule and two molecules of H 2 O in the space between the planes of the anticrown units, is produced. Every water molecule in this supramolecular aggregate is cooperatively bound through the oxygen atom by three Lewis acidic Hg sites of the neighboring anticrown, whereas one of the water protons forms the hydrogen bond with the oxygen atom of the crown ether. An additional contribution in the bonding is made by the interaction of one of the Hg centers of each anticrown unit with the nearest oxygen atom of [12]crown-4. The complex of analogous composition and close structure is formed in the reaction of 1 with aqueous [18]crown-6. However in this sandwich, {[(o-C 6 F 4 Hg) 3 ] 2 ([18]crown-6)(H 2 O) 2 } (6), both protons of each water species are involved in the formation of the H-bonds with the crown ether, while the bonding of each mercuramacrocycle to the crown ether is accomplished due to the coordination of two of its Hg atoms with two oxygen atoms of the crown compound. From the interaction of 1 3 EtOH with 1,3,5-trioxane, a 1:1 complex, {[(o-C 6 F 4 Hg) 3 ](CH 2 O) 3 } (7), having a cage structure, has been isolated. The synthesized adducts are the first complexes of crown ethers with an anticrown.

Photochemical properties of a series of bifunctional monosubstituted derivatives of cymantrene containing a C-, N-, or O-bound π-allyl group, along with n-donating carbamate, amide, or pyridine fragments were investigated. The results obtained demonstrate that the nature and thermodynamic stability of the cyclopentadienylmanganese dicarbonyl chelates derived from bifunctional monosubstituted cymantrene derivatives depend substantially on both the nature of the functional groups and on their position in the substituent at the Cp ring. Thus, for the six-membered chelates, the thermodynamic stability increases in the series carbamates < amides < pyridines < olefins. Some of the dicarbonyl chelates studied form reversible photochromic systems due to linkage isomerization between different donating groups of the bifunctional substituent and the manganese atom with a wide range of times of thermal isomerization.

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By triple condensation of thiourea or guanidine with 1,ω-bis(2-formylphenoxy)-3-oxapentane and ammonium acetate fi rst representatives of the new class of ethers bis(benzo)aza-14-crown-4 were obtained in 28-73% yield that included as a subunit a symm-perhydrotriazine ring. This reaction also proceeds readily with N-monomethyl-and N-monopropenyl-substituted thioureas affording the corresponding derivatives of triazinoazacrown ether. At the same time urea in the similar condensation does not form the expected perhydrotriazinoazacrown ether. The molecular structure of one perhydroazacrown ether as a complex with a chloroform molecule was established by XRD analysis.

α-Ferrocenylalkylation of azoles or S-nucleophiles with FcCH(R)OH (Fc = ferrocenyl) can be accomplished under acid-free conditions as one-pot process via an intermediate formation of the α-ferrocenylalkyl carbonates FcCH(R) OC(O)OEt. The reaction allows the alkylation of acid sensitive substrates like imidazole derivatives or sodium N,N-diethyldithiocarbamate. The reaction with ambident azoles proceeds as the N-alkylation. Some α-ferrocenylalkyl azoleswere found to exhibit plant growth stimulating or herbicidal effects on corn seeds or act as the herbicide safeners against sulfonylurea herbicides.