Synthesis and characterization of substituted (1,2-naphthalocyaninato)iron compounds and bisaxially coordinated isocyanide complexes

Hanack, Michael; Renz, Guenter; Straehle, J.; Schmid, Siegbert

doi:10.1021/jo00011a012

Cited by 53 publications

(20 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[5] In addition, 1,2-NiDN-TABC exists as a mixture of two isomers (6 and 7), and similarly 1,2-NiDNTAiBC and 1,2-NiTNTAC exist as three (8,9, and 10) and four (2, 3, 4, and 5, Scheme 1) isomers, respectively. Each isomer of 1,2-NiDNTABC and 1,2-NiDNTAiBC was completely separated by TLC and Table 1.…”

Section: Resultsmentioning

confidence: 99%

“…[8] The synthetic route to the C 4h isomer of 1,2-FeNc with bulky substituents, in which steric effects suppressed the formation of the other isomers, was developed by the same group. [9] The first successful separation of all of the possible isomers of 1,2-MgNc by chromatography has been reported recently, together with their 1 H NMR and UV/Vis spectra. [10] Moreover, two geometrical isomers, namely, 1,2-MgNc with C 4h symmetry and 1,2-CoNc with C 2v symmetry, have also been isolated by fractional crystallization and characterized by Xray analysis.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis, Spectroscopic, and Electrochemical Studies of 1,2‐Naphthalene‐Ring‐Fused Tetraazachlorins, ‐bacteriochlorins, and ‐isobacteriochlorins: The Separation and Characterization of Structural Isomers

Макарова

Fukuda

Luk’yanets

et al. 2005

Chemistry A European J

View full text Add to dashboard Cite

1,2-Naphthalene-ring-expanded tetraazachlorins (TACs), tetraazabacteriochlorins (TABCs), and tetraazaisobacteriochlorins (TAiBCs) have been synthesized. Procedures for the synthesis of the starting materials, that is, derivatives of 1,2-naphthalenedicarboxylic acid, have been reinvestigated and improved. Nine possible derivatives, including four, two, and three structural isomers of TACs, TABCs, and TAiBCs, respectively, were separated by using thin-layer chromatography (TLC) or high-performance liquid chromatography (HPLC), and the structure of each isomer was determined by (1)H NMR spectroscopy combined with the NOE technique. The formation ratio of each isomer was rationalized in terms of the intramolecular steric repulsion effect, which was predicted by geometry optimizations at the DFT level. The derived compounds were characterized by using IR, electronic, and magnetic circular dichroism (MCD) spectroscopy, and by electrochemical methods. Frequency calculations at the DFT level correctly reproduced the experimental IR spectra and, in particular, distinguished between the three isomers of the TAiBCs. In the electronic absorption and MCD spectra of the TAC and TABC species, the Q-band splits into two intense components similarly to the 2,3-naphthalene-fused derivatives described in our preceding paper, although no significant spectral differences were observed from species to species. On the other hand, the spectra of the TAiBCs showed moderate differences depending on the structure of the isomer. The spectroscopic properties as well as the electrochemical behavior of these chlorins resemble those of the corresponding benzene-fused derivatives rather than the 2,3-naphthalene-fused derivatives. Molecular-orbital and configuration-interaction calculations within the framework of the ZINDO/S method were helpful in the discussions of the above observations.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis, Spectroscopic, and Electrochemical Studies of 1,2‐Naphthalene‐Ring‐Fused Tetraazachlorins, ‐bacteriochlorins, and ‐isobacteriochlorins: The Separation and Characterization of Structural Isomers

Макарова

Fukuda

Luk’yanets

et al. 2005

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…Although the 2,9,16,23-tetraneopentoxyphthalocyaninato zinc(I1) (16) and 2,9,17,24-tetra-tert-butylphthalocyaninato zinc(I1) (17) were produced as pure isomers; several reaction steps were used and only low yields were obtained. The synthesis of a single isomer of I,2-naphthalocyanine has been achieved (18) due to the steric constraints of the benzo substituents, but other 1,8,15,22-tetrasubstituted phthalocyanines gave mixtures of isomers that in one example could be separated by high performance liquid chromatography (HPLC) (19). In this paper we report the exclusive synthesis of two 1,8,15,22-tetrasubstituted phthalocyanines and their zinc derivatives as pure single isomers in high yields under common conditions.…”

Section: Introductionmentioning

confidence: 99%

The syntheses of 2,9,16,23- and 1,8,15,22-tetrahydroxyphthalocyanines

Leznoff¹,

Hu²,

McArthur³

et al. 1994

Can. J. Chem.

View full text Add to dashboard Cite

, 1990 (1994).2,9,16,23-Tetra-p-n-butylbenzyloxy-, 2,9,16,23-tetradiphenylrnethoxy-, 2,9,16,23-tetramethoxymethoxy-, and 1,8,15,22-tetra-p-n-butylbenzyloxyphthalocyanines were synthesized from the appropriate phthalonitriles. Metal-free phthalocyanines were converted to their zinc derivatives. Cleavage from the appropriate precursor with trifluoroacetic acid produced 2,9,16,23-tetrahydroxyphthalocyanine and 1,8,15,22-tetrahydroxyphthalocyanine and their zinc derivatives. NMR spectroscopy revealed that all the 2,9,16,23-tetrasubstituted phthalocyanines are the usual mixtures of the 2,9,16,23, 2,9,16,24, 2,9,17,24, and 2,10,16,24 isomers, but the two 1,8,15,22-tetrasubstituted phthalocyanines were formed as pure single isomers.CLIFFORD C. LEZNOFF, MOUGANG Hu, COLIN R. MCARTHUR, YONGNIAN Qn' l et JOHAN E. VAN LIER Can. J. Chem. 72, 1990.Utilisant les phtalonitriles approprits comme produits de dCpart, on a synthCtisC les 2,9,16,23-tCtra-p-n-butylbenzyloxy-, 2,9,16,23-tttraphtnylmCthoxy-, 2,9,16,23-tCtramtthoxym6thoxy-et 1,8,15,22-tttra-p-n-butylbenzyloxyphtalocyanines. On a transform6 les phtalocyanines libres de mttal en dCrivts zinciques. Le clivage du prtcurseur approprik avec de l'acide trifluoroacttique conduit h la 2,9,16,23-tttrahydroxyphtalocyanine et h la 1,8,15,22-tCtrahydroxyphtalocyanine et h leurs dCrivts zinciques. La RMN rtvttle que toutes les phtalocyanines tCtrasubstitu6es en 2,9,16,23 sont formCes des mClanges habituels des isombres 2,9,16,23, 2,9,16,24, 2,9,17,24 et 2,10,16,24; toutefois, les deux phtalocyanines substitu6es en 1,8,15,22 sont des isomkres purs.

show abstract

“…As for metal-free 14, the presence of two possible side strap isomers generated two multiplets at 5 gens of the side-straps in addition to two pairs of singlets that arise from the 2'-methylene CH2-OTr and 2'-methyl CH,, hydrogens at 3.66,3.64 and 1.65,1.62 ppm, respectively. The NMR spectrum of 17 was examined in the most detail as it was the most soluble of the bis side-strapped Pcs.…”

Section: Spectroscopic and Physical Propertiesmentioning

confidence: 98%

“…Single isomers of 2,9,16,23-(2), 2,9,17,24-(3), and 1,8,15,22-tetrasubstituted phthalocyanines (4), and a 1,2-naphthalocyanine (5) have been prepared capitalizing on reactive substrates (2) or electronic (3) or steric constraints (4,5) but inethods towards the synthesis of pure 1,11,15,25-tetrasubstituted phthalocyanines have been only briefly reported by us in a preliminary coinmunication (6 Having established that phthalocyanines containing bulky substituents at positions adjacent to the macrocyclic core are readily prepared, we directed our attention towards the preparation of bisphthalonitriles bridged at the 3-position, for eventual dimerization to 1,11,15,25-tetrasubstituted phthalocyanines. Earlier, we had suggested (12) that P-hydrogens on substituents could lead to p-elimination reactions under the basic conditions of PC formation and hence we concentrated our attention on bridging groups containing no hydro, oens at the P-position, particularly P,P-dialkyl groups.…”

Section: Introductionmentioning

confidence: 99%

The use of bisphthalonitriles in the synthesis of side-strapped 1,11,15,25-tetrasubstituted phthalocyanines

Leznoff¹,

Drew²

1996

Can. J. Chem.

View full text Add to dashboard Cite

Nucleophilic aromatic substitution reactions of 3-nitrophthalonitrile yield 3-hydroxyphthalonitrile and 3-neopentoxyphthalonitrile, the latter of which condensed to 1,8,15,22-tetraneopentoxyphthalocyanine as a mixture of isomers. Bisphthalonitriles such as 1,3-bis(2',3'-dicyanophenoxy)-2,2-dipentylpropane, 1,3-bis(2',3'-dicyanophenoxy)-2.2-diethylpropane, 1,3-bis(2',3'-dicyanophenoxy)-2,2-dioctylpropane, and 1,3-bis(Y.3'-dicyanophenoxy)-2-methyl-2-trityloxymethylpropane all gave bis-crown-like 1,11,15,25-tetrasubstituted phthalocyanines as pure compounds when treated with lithium octoxide in I-octanol at 196°C. A host of nine other bisphthalonitriles including 1,5-bis(Y.3'-dicyanophenoxy)-3-oxapentane, 1, l -bis(2',3'-dicy anophenoxy methy l)cyclohexane 1,2-bis(2',3'-dicyanophenoxy methy ])benzene, and 2,5-bis(2',3'-dicyanophenoxymethyl)furan did not dimerize to mononuclear phthalocynaines. The "ge171 dimethyl" effect was suggested as a reason for the successful macrocyclizations.

show abstract

Synthesis and characterization of substituted (1,2-naphthalocyaninato)iron compounds and bisaxially coordinated isocyanide complexes

Cited by 53 publications

References 0 publications

Synthesis, Spectroscopic, and Electrochemical Studies of 1,2‐Naphthalene‐Ring‐Fused Tetraazachlorins, ‐bacteriochlorins, and ‐isobacteriochlorins: The Separation and Characterization of Structural Isomers

Synthesis, Spectroscopic, and Electrochemical Studies of 1,2‐Naphthalene‐Ring‐Fused Tetraazachlorins, ‐bacteriochlorins, and ‐isobacteriochlorins: The Separation and Characterization of Structural Isomers

The syntheses of 2,9,16,23- and 1,8,15,22-tetrahydroxyphthalocyanines

The use of bisphthalonitriles in the synthesis of side-strapped 1,11,15,25-tetrasubstituted phthalocyanines

Contact Info

Product

Resources

About