Approaching supramolecular functionality

Functional molecules require a high degree of complexity which is difficult to achieve by covalent synthesis. This article discusses supramolecular approaches to the creation of larger architectures through noncovalent bonds, self-assembly, and template strategies. It highlights selected examples for the structural and conformational control of function and attempts to identify difficulties and challenges which may arise in future.     

On the Chemistry of a Dibenzohypericin Derivative

Summary.  A hypericin derivative was synthesized in which instead of the methyl groups two benzene rings were condensed to the chromophoric system in order to extend its conjugation. This derivative showed lowered fluorescence and concomitantly enhanced sensitized production of active oxygen species as compared to hypericin. However, in contrast to intuition its long wavelength band remained unshifted in comparison to its parent compound hypericin. Geometry and absorption properties were also investigated by means of semiempirical calculations. Received July 27, 2001. Accepted August 9, 2001     

Syntheses and Properties of Two Heterocyclically Substituted Hypericin Derivatives: 10,11-Dibenzothiazolyl-10,11-didemethylhypericin and 10,11-Dibenzoxazolyl-10,11-didemethylhypericin

Summary. The syntheses of the two heterocyclically substituted title hypericin derivatives were achieved starting either from 6-benzothiazolyl-tri-O-methyl-6-demethylemodin or 6-benzoxazolyl-tri-O-methyl-6-demethylemodin. The use of microwave assisted synthesis for the preparation of these anthraquinone synthons and the chemical as well as photochemical properties of the corresponding unique hypericin derivatives, which might constitute new photodynamic therapy agents, are reported. The tautomeric and stereochemical aspects of these hypericin derivatives were investigated by means of semiempirical calculations (AM1).     

The molecular and crystal structures of two diastereomeric 3,4-dihydropyrromethenones

The molecular and crystal structures of the two racemic diastereomeric 3,4-dihydropyrromethenone derivatives1 and2 of configurations (Z) and (E) were determined at 93 K (1, 2) and at room temperature (1). From an analysis of the crystallographically observed temperature coefficients a pseudorotation flexibility of the pyrrolidinone ring in the crystal is deduced. In both compounds a nearly orthogonal arrangement between the two heterocyclic ring systems is observed, which is ascribed to the steric bulk of the substituents in positions 1 and 3 of the pyrrolidinone ring.Herrn Prof.Josef Schurz zum 60. Geburtstag gewidmet.     

Optically and thermally induced electron transfer pathways in hexakis[4-(N,N-diarylamino)phenyl]benzene derivatives

The optically and thermally induced electron transfer pathways of highly symmetrical (D(3)) hexaarylbenzene systems with six triarylamine redox sites have been investigated. Owing to slightly different local redox potentials, the radical trication could be selectively generated by electrochemical methods. This trication shows a strong intervalence charge-transfer band in the near infrared (NIR) that was measured by spectroelectrochemistry and analysed using multi-dimensional Mulliken-Hush theory. Quantum chemical AM1 CI calculations indicate that there is no optically induced concerted three-electron transfer that transforms the ground state into a state in which all three positively charged triarylamine moieties change place with their neutral neighbours. The potential energy surface of the ground state was constructed by using quadratic potentials. From this potential surface it is apparent that there is also no thermally allowed concerted three-electron transfer pathway. Instead, three consecutive one-electron transfer steps are necessary for this process.     

New SbS2 strings in the BaSb2S4 structure

The new compound BaSb₂S₄ crystallizes in the monoclinic system (space group: $\text{P2}{}_1\text{c}$, No. 14) with a = 8.985(2) Å, b = 8.203(3) Å, c = 20.602(5) Å, β = 101.36(3)°. SbS₃ ψ tetrahedra and ψ-trigonal SbS₄ bipyramids are connected by common corners and edgers to infinite strings. These are arraged cross-wise in sheets perpendicular to the c axis.     

Diastereoface Selectivity During Pthalimidonitrene Additions to (E)-and (Z)-configurated α, β-unsaturated esters,induced by a chiral center in the γ-position

In-situ-generated phthalimidonitrene was added to five α, β-unsaturated esters containing a chiral secondary O-function at C(γ). The additions were fully suprafacial, inasmuch as the (E)-isomers 1 afforded only the trans-aziridines 2 and 3 (J(β, γ) = 4.8?5.1 Hz) and the (Z)-isomers 4 only the cis-aziridines 5 and 6 (8.2?8.5 Hz). The products 2 , 3 , 5 , and 6 where shown to possess the arabino-, xylo-, ribo-, and lyxo- configuration, respectively, by X-ray structure analysis of 2b , 2d , and 6a . The diastereoface selectivity of the nitrene additions, induced by the chiral substructure around C(γ), resulted in more 2 than 3 from 1 , but more 6 than 5 from 4 , which means that the preference of attack at the double bond switches from one side to the other depending on the C=C configuration. The preferences were higher at lower temperature. The aziridines 2a , 2d , and 3d exhibit ¹H-NMR-visible isomerism at the ring N-atom; the major (78?95 %)invertomer A is always the one with the phthalimido group in trans-position to the (larger) substructure around C(γ). The other aziridines only show ¹H-NMR signals of one invertomer, which – by steric reasoning - ought to be A ; this is confirmed by a ¹H-NMR argument for 3a , 5a , 6a , 5c , and 6c .     

Reaction of 1,4-pentadiyne with diethylaminotrimethylstannane

The reaction between 1,4-pentadiyne and diethylaminotrimethylstannane leads predominantly to (E)-2-diethylamino-4-trimethylstannyl-2,4-pentaenyne (with either a 1/1 or 1/2 mol ratio of 1,4-pentadiyne and diethylaminotrimethylstannane). With 1/2 stoicheiometry 1,1,5-tris(trimethylstannyl)penta-1,2-dien-4-yne is formed as a minor product. ¹³C and ¹¹⁹Sn NMR data are reported.