A novel class of cationic fused-ring conjugated pyrrole derivatives and their applications in the pharmaceutical field

Abstract

This invention relates to a novel class of cationic fused-ring conjugated pyrrole derivatives and their applications in the pharmaceutical field, characterized by having the following structures (I) and (II): Specifically, this invention relates to a class of novel cationic fused-ring conjugated pyrrole derivatives with advantages such as structural stability, low aggregation resistance, good amphiphilicity, strong absorption in the near-infrared region, high photodynamic activity, and wide applicability. These compounds can be used as photosensitizing drugs or reagents for the diagnosis and treatment of microbial infections, tumors, macular degeneration, actinic keratosis, port-wine stains, condyloma acuminata, and other diseases. They can also be used as fluorescent dyes and reagents in near-infrared fluorescence imaging, fluorescent labeling, or optoelectronic materials.

Description

Technical Field

[0001] This invention relates to the fields of cationic photosensitizing drugs and photodynamic antibacterial (PACT) and photodynamic therapy (PDT), specifically to a class of novel cationic fused-ring conjugated pyrrole derivatives with advantages such as structural stability, non-aggregation, good amphiphilicity, strong absorption in the near-infrared region, high photodynamic activity, and wide applicability, and their applications in the pharmaceutical field. Background Technology

[0002] Photodynamic therapy (PDT), a novel treatment method that combines photosensitizers (photosensitive drugs) and visible light to generate highly reactive oxygen species, thereby inactivating pathogenic microorganisms or cancerous tissues, is now commonly used in photodynamic antibacterial therapy (PACT) and photodynamic therapy (PDT). Compared with traditional therapies, PACT has many advantages such as good selectivity, non-toxicity, reusability, and strong effects. Among them, the most important is that it causes oxidative damage to surrounding tissues through reactive oxygen species, which is non-specific, so microorganisms or diseased tissues will not develop resistance to photosensitizing drugs. With the development of new photosensitizers and the advancement of laser technology, PACT and PDT have become the most promising new treatment technologies for the eradication of some highly resistant bacteria, fungi, viruses, and refractory tumors (Jpn.J.Cancer Res.,2000,91(5):560–565).

[0003] Photodynamic therapy operates at the molecular level through two mechanisms: Type I and Type II. After irradiation with a light source of a specific wavelength, the photosensitizer molecule first transitions from its ground state to a short-lived singlet excited state, and then reaches a longer-lived triplet excited state via intersystem crossing. The triplet excited state photosensitizer molecule directly reacts with the substrate through hydrogen extraction or electron transfer reactions, generating free radicals or free radical ions. These free radicals then react with biomolecules and oxygen molecules to generate oxidation products; this process is called the Type I mechanism, also known as the free radical mechanism. The triplet excited state photosensitizer molecule can also undergo energy transfer with oxygen to generate singlet oxygen (…). 1 O2), highly active 1O2 rapidly reacts with neighboring biomolecules, causing damage; this process is called the type II mechanism, also known as the singlet oxygen mechanism. In the fields of antibacterial or anticancer, the type I mechanism mainly occurs in the cell membrane, such as reacting with unsaturated phospholipid molecules to extract hydrogen, which then reacts further with oxygen to generate lipid peroxides. Lipid peroxidation leads to the disruption of the cell membrane's structural integrity (J. Photochem. Photobiol. B., 1990, 6, 343-347). The type II mechanism, on the other hand, can interact with other target molecules in bacteria or cancer cells, including some amino acids, peptides, enzymes, and receptors. Generally, the type II mechanism is considered the main pathway of photodynamic oxidative killing; therefore, the singlet oxygen quantum yield of photosensitizer molecules is an important factor affecting their photodynamic effect.

[0004] Over the past few decades, research on PDT has mainly focused on cancer treatment, and it has gradually evolved into a new generation of anti-cancer methods following radiotherapy and chemotherapy. In addition, PDT has also been successfully applied to the clinical treatment of other diseases, such as rheumatoid arthritis, atherosclerotic plaques, and actinic keratosis.

[0005] Bacterial and fungal infections can harm human health. Bacteria are pathogens of many diseases, causing tuberculosis, gonorrhea, anthrax, syphilis, plague, trachoma, and other diseases. Fungi can invade human skin, mucous membranes, and deep tissues, causing inflammation and even systemic disseminated infections. Currently, antibiotics are the commonly used treatment method. However, because bacteria and fungi can develop resistance to antibiotics, their effectiveness is significantly reduced. There is an urgent need to research new methods, technologies, and drugs to kill bacteria and fungi. With the development of photosensitizers and advanced optical technologies, PACT (photosensitive active ingredient) is considered one of the most promising antibacterial treatment methods, especially for infections caused by highly resistant bacteria and fungi. PACT has many advantages, such as being non-invasive, having a broad antibacterial spectrum, being effective against biofilms formed by microorganisms, and being effective against deep gingival infections caused by dental implants.

[0006] In the field of photodynamic antibacterial therapy, photosensitizers such as toluidine blue (TBO) or methylene blue (MB) are currently the most commonly used. Both are phenothiazine basic dyes, and studies have found that these dyes can be used in photodynamic antimicrobial therapy. TBO-mediated PACT has entered the in vivo research stage and has achieved good therapeutic effects; however, its high permeability leads to significant side effects, limiting its application in in vivo therapy (Lasers. Med. Sci., 2009, 24(4): 521-526). MB has been extensively studied in the medical field and has been successfully applied in vitro against bacteriophage and viral infections (Proc. Soc. Exp. Biol. Med., 1928, 26, 100-101); in addition, Creagh et al. reported that high concentrations of MB can also be used to treat bladder cancer, but due to its strong photobleaching phenomenon, its application in in vivo against tumors is greatly limited (Br. J. Urol., 1995, 75(4): 477-479). Currently, there is no multi-purpose photosensitizer drug that can be used for both anti-tumor and antimicrobial purposes. Developing a widely applicable photosensitizer (that can be used for PDT and PACT) is an important goal pursued by medical scientists.

[0007]

[0008] Due to the drawbacks of phenathiazide derivatives, such as weak absorption intensity, low singlet oxygen generation capacity, significant photobleaching phenomenon, and large side effects, researchers have begun to focus on other types of photosensitizers. Fluoroboron dipyrrole compounds (BODIPY, C-BDP) are a class of organic fluorescent dyes with ultraviolet-visible absorption wavelengths between 400-500 nm. In recent years, research on these molecules has mainly focused on fluorescence, with limited research on their application in photodynamic anticancer and antibacterial applications. Banfi et al. modified the structure of fluoroboron dipyrrole to design a water-soluble BODIPY-type dye molecule (compound 1). Its maximum absorption wavelength is at 550 nm, and its oil-water partition coefficient logP value is -1.96, exhibiting good photodynamic activity and a good sterilization effect. However, the low maximum absorption wavelength of this molecule limits its application in the field of photodynamic antibacterial (J. Photochem. Photobiol. B., 2012, 114, 44-51). To increase the maximum absorption wavelength of the BODIPY molecule, Li Chao et al. increased the degree of conjugation of the molecule at the 3 and 7 positions of fluoroboronpyrrole through the Heck reaction, preparing a conjugated pyridine salt BODIPY derivative (compound 2). This resulted in a red shift of the maximum absorption wavelength of the compound to 630 nm, and it also exhibited a certain sterilization effect. However, the molecule has poor stability and does not have the potential to be used for photodynamic antibacterial purposes (Chem. Phys. Chem., 2012, 13, 2739). In addition, O'Shea et al. designed and synthesized an aza-BODIPY-type photosensitive molecule (compound 3). The molecule has a maximum absorption wavelength of 643 nm, introduces two quaternary ammonium ions, significantly improves water solubility, has a LogP value of -0.23, and has good amphiphilicity. It showed high photodynamic antibacterial ability against both Gram-negative and Gram-positive bacteria. However, this molecule also has the disadvantage of poor in vivo stability, which greatly limits its application in the field of photodynamic therapy (J.Med.Chem.,2010,53(20):7337-7343).

[0009]

[0010] Currently, BODIPY-type photosensitizers generally suffer from many drawbacks, such as structural instability, weak absorption in the near-infrared region, poor photodynamic effects, and easy aggregation. Building upon previous research, we have innovatively designed and prepared novel cationic thieno[3,2-b]thiophene fused-ring BODIPY derivatives with a phenyl group at the mesentery. The introduction of the thiophene fused ring expands the conjugated system of the BODIPY parent ring, increasing the maximum absorption wavelength range of this class of compounds to 650-730 nm. Introducing cationic groups (such as quaternary ammonium and quaternary phosphorus) around the benzene ring significantly improves the water and lipid solubility of the compounds, greatly expanding the logP value range of BODIPY photosensitizing drug molecules (-0.1 to 7.5). This allows these novel cationically modified thieno[3,2-b]thiophene fused-ring BODIPY derivatives to be flexibly used in cancer and antibacterial treatments. The photosensitizing drug molecules designed and synthesized by our team have advantages such as higher photodynamic activity, strong reproducibility, good amphiphilicity, and wide range of applications. They can be developed into photodynamic therapy drugs for treating diseases caused by microbial infections, as well as diseases such as tumors, macular degeneration, actinic keratosis, port-wine stains, and condyloma acuminata. They are also expected to be developed into multi-purpose photodynamic drug candidates with both PACT and PDT effects. Summary of the Invention

[0011] To overcome the shortcomings of existing photosensitizers or photosensitizing drugs, such as complex composition, unstable structure, easy aggregation, weak absorption in the near-infrared region, poor amphiphilicity, and limited applications, this invention employs a total synthesis method to prepare novel cationic pyrrole-containing fused-ring conjugated derivatives with a phenyl group at the mesentery. Cationic groups are introduced around the benzene ring, and halogen atoms are introduced around the conjugated parent ring. These new compounds exhibit significantly enhanced absorption in the near-infrared region, significantly improved singlet oxygen yield, significantly enhanced photodynamic effects, and strong structural stability. After extensive creative work, a novel cationically modified thieno[3,2-b]thiophene fused-ring conjugated derivative was synthesized, thus completing this invention.

[0012] This invention relates to a class of novel cationic fused-ring conjugated pyrrole derivatives with advantages such as structural stability, non-aggregation, good amphiphilicity, strong absorption in the near-infrared region, high photodynamic activity, and wide applicability, and their applications in the pharmaceutical field.

[0013] The invention is summarized as follows:

[0014] A novel class of cationic fused-ring conjugated pyrrole derivatives characterized by stable structure, low aggregation, good amphiphilicity, strong absorption in the near-infrared region, high photodynamic activity, and wide applicability, is characterized in that: the photosensitizer is a thieno[3,2-b]thiophene fused-ring conjugated derivative (I) and (II) with a cation-modified mesentery position.

[0015]

[0016] Where A is an alkyl group, an alkyl group containing N, O, or S atoms, an alkyl group containing carbonyl groups, an alkyl group containing amide bonds, or any alkyl group containing alkane, carboxyl (ester) group, hydroxyl, or amino side chains;

[0017] Where Y = Cl,Br,I;

[0018] X is H, Cl, Br, I. Where Z = O, S, Se;

[0019] R 2 ,R 3 ,R 4 =-H,-F,-Cl,-Br,-I,-OH,-O(CH2) m CH3,-(CH2) m CH3,-(CH2) m O(CH2) n C(CH3)3,

[0020] -(CH2) m O(CH2) n CH(CH3)2,-(CH2) m COOH,-(CH2) m CH(CH3)COOH, -(CH2) m C(CH3)2COOH,

[0021] -(CH2) m OH,-(CH2) m C6H4OH,-(CH2) m CO(CH2) n OH,-(CH2) m O(CH2) n OH,-(CH2) m (OCH2CH2) p OH,-(CH2) m R 1 ,-(CH2) m C(CH3)2R 1 ,-(CH2) m CH(CH3)R 1 ,-(CH2) m O(CH2) n R 1 ,-(CH2) m S(CH2) n R 1 ,

[0022] -(CH2) m O(CH2)m C(CH3)2R 1 ,-(CH2) m O(CH2) m CH(CH3)R 1 ,-(CH2) m S(CH2) m C(CH3)2R 1 ,

[0023] -(CH2) m S(CH2) m CH(CH3)R 1 ,-(CH2) m (OCH2CH2) p R 1 ,-(CH2) m CO(CH2) m C(CH3)2R 1 ,

[0024] -(CH2) m CO(CH2) m CH(CH3)R 1 ,-(CH2) m CONH(CH2) n R 1 ,-(CH2) m CONH(CH2) n C(CH3)2R 1 ,

[0025] -(CH2) m CONH(CH2) n CH(CH3)R 1 Or amino acid derivatives, m = 0-7, n = 1-7, p = 1-5.

[0026] According to formulas (I) and (II) of claim 1, wherein

[0027] A is -(CH2) n -,-(CH2) m C(CH3)2-,-(CH2) m CH(CH3)-,-(CH2) m O(CH2) n -,-(CH2) m S(CH2) n -,

[0028] -(CH2) m O(CH2) m C(CH3)2-,-(CH2) mO(CH2) m CH(CH3)-,-(CH2) m S(CH2) m C(CH3)2-,

[0029] -(CH2) m S(CH2) m CH(CH3)-,-(CH2) m (OCH2CH2) p -,-(CH2) m CO(CH2) m C(CH3)2-,

[0030] -(CH2) m CO(CH2) m CH(CH3)-,-(CH2) m CONH(CH2) n -,-(CH2) m CONH(CH2) n C(CH3)2-,

[0031] -(CH2) m CONH(CH2) n CH(CH3)-,-R 5 (CH2) m C(CH3)2-,-R 5 (CH2) m CH(CH3)-,-R 5 O(CH2) n -,

[0032] -R 5 O(CH2) m C(CH3)2-,-R 5 O(CH2) m CH(CH3)-,-R 5 (OCH2CH2) p -,-R 5 CO(CH2) m CH(CH3)-,

[0033] -R 5 CO(CH2) m C(CH3)2-,m = 0 - 7,n = 1 - 7,p = 1 - 5;

[0034] Where R 5 is -CH[(CH2) m CH3],-CH[(CH2) n OCH3],-CH[(CH2)n OH],-CH[(CH2) m COOH],

[0035] -CH[(CH2) m O(CH2) n C(CH3)3],-CH[(CH2) m COO(CH2) m CH3],-CH[(CH2] m (OCH2CH2) n CH3)],

[0036] -CH[(CH2) m CO(CH2) n C(CH3)3],-CH[(CH2) m CO(CH2) n [CH(CH3)2],

[0037] -CH[(CH2) m CONH(CH2) n C(CH3)3]-CH((CH2) m CONH[CH2) n [CH(CH3)2], m=0-7, n=1-7.

[0038] According to claim 1, the amino acid derivative is:

[0039] -(CH2) m CONH(CH2) n COOH,-(CH2) m CONHCH(CH3)COOH,

[0040] -(CH2) m CONH(CH2) n CO(CH2) p COOH,-(CH2) m CONHCH[CH(CH3)2]COOH,

[0041] -(CH2) m CONHCH[CH2CH(CH3)2]COOH,-(CH2) m CONHCH[CH(CH3)CH2CH3]COOH,

[0042] -(CH2) m CONHCH(CH2C6H5)COOH,-(CH2) m CON[(CH2) nCOOH]2,

[0043] -(CH2) m CONHCH(COOH)CH2COOH, m=0-7, n=1-7, p=1-5.

[0044] According to claim 1, a novel class of cationic fused-ring conjugated pyrrole derivatives (I) is characterized in that the class of compounds includes the following compounds:

[0045] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(N,N,N-triethyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene (I1);

[0046] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(N,N-diethyl-N-methyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene (I2);

[0047] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(pyridyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene (I3);

[0048] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(quinolinyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene (I4);

[0049] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(triphenylphosphonium)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene (I5);

[0050] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[4-(2-(N,N,N-triethyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene (I6);

[0051] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[4-(2-(N,N-diethyl-N-methyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene (I7);

[0052] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[4-(2-(pyridyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene (I8);

[0053] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[4-(2-(quinolinyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene (I9);

[0054] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[4-(2-(triphenylphosphonium)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (I 10 );

[0055] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(N,N,N-triethyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenzatetraene (I 11 );

[0056] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(N,N-diethyl-N-methyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenzatetraene (I 12 );

[0057] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(pyridyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (I 13 );

[0058] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(quinolinyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (I 14 );

[0059] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(triphenylphosphonium)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenzatetraene (I 15 );

[0060] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[4-(2-(N,N,N-triethyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpatene (I 16 );

[0061] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(N,N-diethyl-N-methyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpatene (I 17 );

[0062] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[4-(2-(pyridyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (I 18 );

[0063] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[4-(2-(quinolinyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (I 19 );

[0064] 2,3;5,6-Di[2-bromothiophene[3,2-b]thiophene]-4,4-difluoro-8-[4-(2-(triphenylphosphonium)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (I 20 ).

[0065] According to claim 1, a novel class of cationic fused-ring conjugated pyrrole derivatives (II) is characterized in that the class of compounds includes the following compounds:

[0066] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,5-di(2-(N,N,N-triethyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene(II1);

[0067] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,5-di(2-(N,N-diethyl-N-methyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene(II2);

[0068] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,5-di(2-(pyridyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene(II3);

[0069] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,5-di(2-quinolinyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene(II4);

[0070] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,5-di(2-(triphenylphosphonium)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene(II5);

[0071] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-di(2-(N,N,N-triethyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene(II6);

[0072] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-di(2-(N,N-diethyl-N-methyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene (II7);

[0073] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-di(2-(pyridyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene(II8);

[0074] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-di(2-(quinolinyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene (II9);

[0075] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-di(2-(triphenylphosphonyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene (II) 10 );

[0076] 2,3;5,6-Di[2-thienyl-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-tris(2-(N,N,N-triethyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene (II) 11 );

[0077] 2,3;5,6-Di[2-thienyl-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-tris(2-(N,N-diethyl-N-methyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene (II) 12 );

[0078] 2,3;5,6-Di[2-thienyl-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-tris(2-(pyridyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 13 );

[0079] 2,3;5,6-Di[2-thienyl-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-tris(2-(quinolinyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 14 );

[0080] 2,3;5,6-Di[2-thienyl-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-tris(2-(triphenylphosphonyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenzatetraene (II) 15 );

[0081] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,5-di(2-(N,N,N-triethyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenzatetraene (II) 16 );

[0082] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,5-di(2-(N,N-diethyl-N-methyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 17 );

[0083] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,5-di(2-(pyridyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenzatetraene (II) 18 );

[0084] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,5-di(2-(quinolinyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 19 );

[0085] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,5-di(2-(triphenylphosphonium)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenzatetraene (II) 20 );

[0086] 2,3;5,6-Di[2-bromothiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-di(2-(N,N,N-triethyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 21 );

[0087] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-di(2-(N,N-diethyl-N-methyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 22 );

[0088] 2,3;5,6-Di[2-bromothiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-di(2-(pyridyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 23 );

[0089] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-di(2-(quinolinyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 24 );

[0090] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-di(2-(triphenylphosphonyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene (II) 25 );

[0091] 2,3;5,6-Di[2-(2-bromo-thienyl)-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-di(2-(N,N,N-triethyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene (II) 26 );

[0092] 2,3;5,6-Di[2-(2-bromo-thienyl)-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-tris(2-(N,N-diethyl-N-methyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indentraene (II) 27 );

[0093] 2,3;5,6-Di[2-(2-bromo-thienyl)-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-tris(2-(pyridyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 28 );

[0094] 2,3;5,6-Di[2-(2-bromo-thienyl)-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-tris(2-(quinolinyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 29 );

[0095] 2,3;5,6-Di[2-(2-bromo-thienyl)-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-tris(2-(triphenylphosphonyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene (II) 30 );

[0096] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,4,5-tris(2-(N,N,N-triethyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 31 );

[0097] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,4,5-tris(2-(N,N-diethyl-N-methyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 32 );

[0098] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,4,5-tris(2-(pyridyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 33 );

[0099] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,4,5-tris(2-(quinolinyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 34 );

[0100] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,4,5-tris(2-(triphenylphosphonium)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenzatetraene (II) 35 );

[0101] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,4,5-tris(2-(N,N,N-triethyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 36 );

[0102] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,4,5-tris(2-(N,N-diethyl-N-methyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 37 );

[0103] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,4,5-tris(2-(pyridyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 38 );

[0104] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,4,5-tris(2-(quinolinyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 39 );

[0105] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,4,5-tris(2-(triphenylphosphonyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene (II) 40 );

[0106] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,4,5-tris(2-(N,N,N-triethyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenzatetraene (II) 41 );

[0107] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,4,5-tris(2-(N,N-diethyl-N-methyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenzatetraene (II) 42 );

[0108] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,4,5-tris(2-(pyridyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenzatetraene (II) 43 );

[0109] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,4,5-tris(2-(quinolinyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 44 );

[0110] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,4,5-tris(2-(triphenylphosphonium)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenzatetraene (II) 45 )

[0111] 2,3;5,6-Di[2-bromothiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,4,5-tris(2-(N,N,N-triethyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 46 );

[0112] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,4,5-tris(2-(N,N-diethyl-N-methyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 47 );

[0113] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,4,5-tris(2-(pyridyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 48 );

[0114] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,4,5-tris(2-(quinolinyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 49 );

[0115] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,4,5-tris(2-(triphenylphosphonyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene (II) 50 ).

[0116] The novel cationic fused-ring conjugated pyrrole derivatives (I) and (II) described in claim 1 can be used as photosensitizing drugs or reagents for the diagnosis and treatment of diseases such as microbial infections, tumors, macular degeneration, actinic keratosis, port-wine stains, and condyloma acuminata. They can also be used as fluorescent dyes and reagents in the fields of near-infrared fluorescence imaging, fluorescent labeling, or optoelectronic materials.

[0117] Specific preparation scheme

[0118] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0119] [Example 1]

[0120] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(N,N,N-triethyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene (I1)

[0121]

[0122] Thiophene[3,2-b]pyrrole III1 (1.09 g, 6.1 mmol) and 4-(3-(N,N,N-triethyl)propyl)carbamoylbenzaldehyde II1 (500 mg, 3.0 mmol) were added sequentially to a three-necked flask. DCM (100 mL) was added, and under argon atmosphere, one drop of trifluoroacetic acid was added dropwise. The mixture was stirred at room temperature for 24 hours, then DDQ (1.04 g, 4.5 mmol) was added, and stirring was continued for 1.5 hours. After a few hours, triethylamine (10 mL) and boron trifluoride ether solution (8 mL) were added sequentially, and the mixture was stirred for another hour. The reaction was confirmed to be complete by TLC. The reaction mixture was washed with saturated saline solution (30 mL × 3), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate in the organic layer, filtered, and the solvent was evaporated under reduced pressure. The crude product was purified by column chromatography (DCM:MeOH = 20:1) to obtain a dark blue solid I1 (462 mg, 30.2%).

[0123] 1 H NMR(400MHz, DMSO-d6)δppm:7.99-7.93(m,2H),7.45-7.39(m,2H),7.30(dd,J=10.1,7.5Hz,2H),7.12(d,J=7.5Hz,1H),6.95(d,J=7.3Hz,1H), 6.75(s,1H),6.30(s,1H),6.20(s,1H),3.64(td,J=6.9,1.0Hz,2H),3.54(td,J=6.9,1.0Hz,2H),3.28(q,J=8.0Hz,6H),1.25(t,J=8.0Hz,9H). 13 C NMR(101MHz,DMSO-d6)δppm:168.55,163.85,162.49,151.63,150.53,148.14,145.92,143.38,143.33,142.79,139.03,1 34.89,129.85,128.96,128.57,127.06,123.30,122.06,102.71,54.14,53.55,25.52,9.32.MS(MALDI-TOF):calculated for C 32 H 30 BBr F2N4OS4[M-Br+H]:663.1379; found,664.4567.

[0124] [Example 2]

[0125] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(N,N,N-triethyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenzatetraene (I 11 )

[0126]

[0127] Compound I1 (500 mg, 1 mmol) was dissolved in a mixed solvent of tetrahydrofuran (20 mL), and a methanol solution of NBS (150 mg, 2 mmol) was slowly added dropwise. The reaction mixture was stirred at 0 °C for 12 hours. TLC was used to monitor the disappearance of the starting material and the formation of the product. The reaction was quenched by adding sodium thiosulfate solution (5 mol / L, 5 mL). After removing the solvent under reduced pressure, the product was recrystallized from dichloromethane and methanol to obtain a dark green powder I1. 11 (600mg, 90.2%). 1 H NMR (400MHz, DMSO-d6) δppm: 13.40 (s, 1H), 8.12 (dd, J = 12.3, 6.3Hz, 4H), 7.70 (d, J = 7.3Hz, 2H), 7.22 (s, 2H). 13 C NMR (101MHz, DMSO-d6): δppm168.14,167.94,167.88,167.83,162.08,16 1.85,161.79,161.74,156.72,156.67,156.61,151.68,151.63,151.57,1 51.08,150.59,145.26,144.81,143.38,129.51,128.20,128.16,128.05,122.90,119.88,117.08,116.15,101.85.HRMS(MALDI-TOF):calculated forC 32 H 28 BBr3F2N2O2S4[M-Br+H]:821.3574.8045; found:823.2043.

[0128] [Example 3]

[0129] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(pyridyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene (I3)

[0130]

[0131] Compound I3 was prepared using the same synthetic method as compound I1.

[0132] 1 H NMR (400MHz, DMSO-d6) δppm: 9.38 (dt, J=7.0, 1.4Hz, 2H), 8.74 (t, J=7.3, 1.5Hz, 1H), 8.28-8.18 (m, 3H), 7.99-7.93 (m, 2H), 7.45-7.37 (m, 4H), 7.1 9(d,J=7.5Hz,1H),7.13(d,J=7.5Hz,1H),6.94(d,J=7.5Hz,1H),6.30(s, 1H), 5.01(t,J=7.1Hz,2H), 3.48(t,J=7.1Hz,2H), 2.33(p,J=7.1Hz,2H). 13 C NMR(101MHz,DMSO-d6)δppm:168.55,166.26,162.49,156.67,156.46,151.63,150.59,148.14,146.47,145.26,144.56,143.68,143.3 8,139.03,136.07,129.88,128.93,127.10,127.07,122.38,116.62,116.49,101.85,61.31,39.36,29.33.MS(MALDI-TOF):calculated for C 31 H 20 BBrF2N4OS4[M-Br+H]:641.34; found,642.60.

[0133] [Example 4]

[0134] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(quinolinyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene (I4)

[0135]

[0136] Compound I4 was prepared using the same synthetic method as compound I1.

[0137] 1H NMR (400MHz, DMSO-d6) δppm: 9.38 (dd, J=7.4, 1.5Hz, 1H), 8.65–8.57 (m, 2H), 8 .42(dt,J=7.5,1.6Hz,1H),8.27-8.18(m,3H),8.03-7.93(m,3H),7.45-7.37( m,4H),7.19(d,J=7.5Hz,1H),7.13(d,J=7.5Hz,1H),6.94(d,J=7.5Hz,1H),6. 30(s,1H),5.01(t,J=7.1Hz,2H),3.48(t,J=7.1Hz,2H),2.33(p,J=7.1Hz,2H). 13 C NMR(101MHz,DMSO-d6)δppm:168.55,166.26,162.49,156.46,151.63,150.59 ,148.14,145.26,143.68,143.38,142.57,139.03,138.97,137.02,136.07,13 2.37,129.88,129.14,128.93,127.10,127.07,126.62,126.40,124.60,122. 38,116.62,116.49,101.85,59.08,39.36,29.14.MS(MALDI-TOF):calculated for C 35 H 22 BBrF2N4OS4[M-Br+H]:771.0366; found,772.1276.

[0138] [Example 5]

[0139] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(triphenylphosphonium)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene (I5)

[0140]

[0141] Compound I5 was prepared using the same synthetic method as compound I1.

[0142] 1H NMR (400MHz, DMSO-d6) δppm: 8.20 (s, 1H), 7.96 (d, J = 7.5Hz, 2H), 7.45-7.29 (m, 9H), 7.32-7.22 (m, 11H), 7.19 (d, J = 7.5Hz, 1H), 7.1 3(d,J=7.5Hz,1H),6.94(d,J=7.5Hz,1H),6.30(s,1H),3.48(t,J=7.1Hz,2H),1.60(p,J=7.0Hz,2H),1.30(dt,J=14.0,7.1Hz,2H). 13 C NMR(101MHz,DMSO-d6)δppm:168.55,166.26,162.49,156.67,156.46,151.63 ,150.59,148.14,145.26,143.68,143.38,139.03,136.07,133.47,132.97,1 31.66,131.57,129.88,127.10,127.07,122.38,119.79,119.08,116.62,116 .49,101.85,41.44,41.29,23.59,23.18,22.40.MS(MALDI-TOF):calculated for C 44 H 30 BBrF2N3OPS4[M-Br+H]:824.1279; found,824.2195.

[0143] [Example 6]

[0144] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[4-(2-(N,N,N-triethyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene(I6)

[0145]

[0146] Compound I6 was prepared using the same synthetic method as compound I1.

[0147] 1H NMR(400MHz, DMSO-d6)δppm:7.40(t,J=3.8Hz,2H),7.35–7.29(m,2H),7.19(d,J=7.5Hz,1H),7.13(d,J=7.5Hz,1H),6.94(d,J=7.5 Hz,1H),6.79-6.73(m,2H),6.30(s,1H),4.38(t,J=7.1Hz,2H),3.66(t,J=7.1Hz,2H),3.28(q,J=8.0Hz,6H),1.25(t,J=8.0Hz,9H). 13 C NMR (101MHz, DMSO-d6) δppm: 166.26, 162.49, 157.48, 156.46, 151.63, 150.59, 148.14, 145.26, 143.38, 139.26, 136. 07,135.44,127.07,122.38,116.62,116.49,113.47,101.85,66.01,54.53,53.55,9.32.MS(MALDI-TOF):calculated forC 31 H 29 BBrF2N3OS4[M-Br+H]:716.2128; found,717.2512.

[0148] [Example 7]

[0149] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,5-di(2-(N,N,N-triethyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene(II1)

[0150]

[0151] Compound II1 was prepared using the same synthetic method as compound I1.

[0152] 1H NMR (400MHz, DMSO-d6) δppm: 8.34(t,J=2.0Hz,1H),8.04(d,J=2.0Hz,2H),7.40(t,J=3.7Hz,2H),7.19(d,J=7.5Hz,1H),7.13(d,J=7.5Hz,1H),6.94( d,J=7.5Hz,1H),6.75(s,2H),6.30(s,1H),3.64(td,J=6.9,1.0Hz,4H),3. 54(td,J=6.9,1.0Hz,4H), 3.28(q,J=8.0Hz,12H), 1.25(t,J=8.0Hz,18H). 13 C NMR(101MHz,DMSO-d6)δppm:166.93,156.46,150.59,148.14,146.64,143.38,136.83,136.07,132.15,130.83 ,127.07,126.34,122.38,116.62,116.49,101.85,54.00,53.55,40.11,9.32.MS(MALDI-TOF):calculatedfor C 41 H 49 BBr2F2N6O2S4[M-2Br+H]:834.2179; found,835.2395.

[0153] [Example 8]

[0154] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,5-di(2-(N,N-diethyl-N-methyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene(II2)

[0155]

[0156] Compound II2 was prepared using the same synthetic method as compound I1.

[0157] 1 H NMR (400MHz, DMSO-d6) δppm: 8.58 (t, J = 1.9 Hz, 1H), 8.31 (d, J = 2.0 Hz, 2H), 7.40 (s, 1H), 6.80 (d, J = 4.9 Hz, 2H), 6.30 (s, 1H). 13C NMR(101MHz,DMSO-d6)δppm:167.94,167.88,167.83,167.68,162.08,161.85,161.79,161.74,156.72,156.67,156.61,152.11,152.05,152.00, 151.08,150.59,146.64,143.38,133.69,131.49,130.71,130.15,128.05,122.90,119.88,117.08,116.15,101.85.MS(MALDI-TOF):calculated forC 39 H 45 BBr2F2N6O2S4[M-2Br+H]:805.2127; found,806.2387.

[0158] [Example 9]

[0159] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,5-di(2-(pyridyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene(II3)

[0160]

[0161] Compound II3 was prepared using the same synthetic method as compound I1.

[0162] 1 H NMR (400MHz, DMSO-d6) δppm: δ9.38 (dt, J=7.1, 1.4Hz, 4H), 8.74 (t, J=7.3, 1.5 Hz,2H),8.34(t,J=2.0Hz,1H),8.28-8.20(m,4H),8.04(d,J=2.0Hz,2H),7.40( t,J=3.8Hz,2H),7.19(d,J=7.5Hz,1H),7.13(d,J=7.5Hz,1H),6.94(d,J=7.5H z,1H),6.75(s,2H),6.30(s,1H),5.33(t,J=7.1Hz,4H),3.94(t,J=7.1Hz,4H). 13C NMR(101MHz,DMSO-d6)δppm:166.93,166.26,162.49,156.67,156.46,152.05,150.59,148.14,146.64,146.47,143.36,136.83 ,136.07,132.15,130.83,128.87,127.07,126.34,122.38,116.62,116.49,101.85,60.84,39.89.MS(MALDI-TOF):calculated for C 39 H 29 BBr2F2N6O2S4[M-2Br+H]:790.1275; found,790.7205.

[0163] [Example 10]

[0164] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-di(2-(N,N,N-triethyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene(II6)

[0165]

[0166] Compound II6 was prepared using the same synthetic method as compound I1.

[0167] 1 H NMR (400MHz, DMSO-d6) δppm:7.40(t,J=3.8Hz,2H),7.19(d,J=7.5Hz,1H),7.13(d,J=7.5Hz,1H),6.94(d,J=7.5Hz,1H),6.61 (d,J=1.9Hz,2H),6.30(s,2H),4.38(t,J=7.1Hz,4H),3.66(t,J=7.1Hz,4H),3.28(q,J=8.0Hz,12H),1.25(t,J=8.0Hz,18H). 13 C NMR(101MHz,DMSO-d6)δppm:162.40,156.46,150.59,148.14,146.64,143.38,136.07,133.24,127.07,1 22.38,116.62,116.49,113.90,105.60,101.85,66.01,54.53,53.55,9.32.MS(MALDI-TOF):calculated for C 39 H 47BBr2F2N4O2S4[M-2Br+H],780.2176; found,781.3212.

[0168] [Example 11]

[0169] 2,3;5,6-Di[2-thienyl-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-tris(2-(N,N,N-triethyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene (II) 11 )

[0170]

[0171] Compound II was prepared using the same synthetic method as compound I1. 11 .

[0172] 1 H NMR (400MHz, DMSO-d6) δppm: 7.53 (dd, J=7.5, 1.5Hz, 1H), 7.17 (dd, J=7.5, 1.5Hz, 1H), 7.08 (d, J=15.0Hz, 1H), 6.85 (t, J=7.5Hz, 1 H), 6.61 (d, J = 2.0Hz, 1H), 6.30 (s, 1H), 4.38 (t, J = 7.1Hz, 2H), 3.66 (t, J = 7.1Hz, 2H), 3.28 (q, J = 8.0Hz, 6H), 1.25 (t, J = 8.0Hz, 9H). 13 C NMR (101MHz, DMSO-d6) δppm: 169.13, 162.40, 158.56, 150.59, 146.64, 143.38, 139.35, 134.26, 133.24, 127.90, 124. 43,124.07,123.36,117.14,113.90,107.73,105.60,101.85,66.01,54.53,53.55,9.32.MS(MALDI-TOF):calculated forC 47 H 51 BBr2F2N4O2S6[M-2Br+H],945.1212; found,946.2109.

[0173] [Example 12]

[0174] 2,3;5,6-Di[2-bromothiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-di(2-(N,N,N-triethyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II)21 )

[0175]

[0176] Refer to compounds I1 and I 11 Compound II was prepared by the synthetic method. 21 .

[0177] 1 H NMR(400MHz,DMSO-d6)δppm:6.80(d,J=4.9Hz,1H),6.61(d,J=1.9Hz,1H),6.30(s,1H),4 .38(t,J=7.1Hz,2H),3.66(t,J=7.1Hz,2H),3.28(q,J=8.0Hz,6H),1.25(t,J=8.0Hz,9H). 13 C NMR(101MHz,DMSO-d6)δppm:162.40,162.08,151.08,150.59,146.64,143.38,133.24,128.05,122.90,1 19.88,117.08,116.15,113.90,105.60,101.85,66.01,54.53,53.55,9.32.MS(MALDI-TOF):calculated for C 47 H 63 BBr4F2N5O3S4[M-2Br+H],938.1191; found,939.2281.

[0178] [Example 13]

[0179] 2,3;5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,5-di(2-(N,N-diethyl-N-methyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 27 )

[0180]

[0181] Refer to compounds I1 and I 11 Compound II was prepared by synthetic method 27 .

[0182] 1H NMR (400MHz, DMSO-d6) δppm: 8.34 (t, J = 2.0Hz, 1H), 8.04 (d, J = 2.0Hz, 2H), 7.40 (s, 1H), 6.80 (d, J = 4.9Hz, 2H), 6.75 (s, 2H), 6.30 (s, 1H), 3.64 (td, J=6.9, 1.0Hz, 4H), 3.54 (td, J=6.9, 1.0Hz, 4H), 3.32-3.24 (m, 14H), 1.25 (t, J=8.0Hz, 12H). 13 C NMR(101MHz,DMSO-d6)δppm:166.93,162.08,151.08,150.59,146.64,143.38,136.83,132.15,130.83,128.05,1 26.34,122.90,119.88,117.08,116.15,101.85,59.86,56.48,46.15,39.98,11.27.MS(MALDI-TOF):calculated for C 39 H 43 BBr4F2N6O2S4[M-2Br+H]:964.3375; found,964.4305.

[0183] [Example 14]

[0184] 2,3;5,6-Di[2-(2-bromo-thienyl)-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-di(2-(N,N,N-triethyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenotetraene (II) 26 )

[0185]

[0186] Refer to compounds I1 and I 11 Compound II was prepared by the synthetic method. 26 .

[0187] 1 H NMR (400MHz, DMSO-d6) δppm: 7.08 (d, J = 15.0Hz, 1H), 6.95 (d, J = 7.5Hz, 1H), 6.90 (d, J = 7.5Hz, 1H), 6.61 (d, J = 2.0 Hz, 1H), 6.30 (s, 1H), 4.38 (t, J = 7.1Hz, 2H), 3.66 (t, J = 7.1Hz, 2H), 3.28 (q, J = 8.0Hz, 6H), 1.25 (t, J = 8.0Hz, 9H).13 C NMR (101MHz, DMSO-d6) δppm: 169.13, 162.40, 158.56, 150.59, 146.64, 143.38, 138.78, 134.73, 133.24, 127.35, 125. 16,121.44,117.14,113.90,110.55,107.73,105.60,101.85,66.01,54.53,53.55,9.32.MS(MALDI-TOF):calculated for C 47 H 49 BBr4F2N4O4S6[M-2Br+H],1102.91; found,1102.81.

[0188] [Example 15]

[0189] 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,4,5-tris(2-(N,N,N-triethyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 31 )

[0190]

[0191] Compound II was prepared using the same synthetic method as compound I1. 31 .

[0192] 1 H NMR (400MHz, DMSO-d6) δppm: 7.40 (t, J = 3.8 Hz, 1H), 6.61 (s, 1H), 4.38 (t, J = 7. 1Hz, 3H), 3.66 (t, J = 7.1Hz, 3H), 3.28 (q, J = 8.0Hz, 9H), 1.25 (t, J = 8.0Hz, 13H). 13 C NMR (101MHz, DMSO-d6) δppm: 156.46, 153.85, 150.59, 148.14, 146.64, 143.38, 140.68, 136.07, 129.68, 127. 07,122.38,116.62,116.49,111.58,101.85,67.36,66.20,54.53,53.55,9.32.MS(MALDI-TOF):calculated for C 47 H 65 BBr3F2N5O3S4[M-3Br+H],925.3211; found,926.3242.

[0193] [Example 16]

[0194] 2,3;5,6-Di[2-bromothiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,4,5-tris(2-(N,N,N-triethyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II) 46 )

[0195]

[0196] Refer to compounds I1 and I 11 Compound II was prepared by the synthetic method. 46 .

[0197] 1 H NMR (400MHz, DMSO-d6) δppm: 6.80 (d, J = 4.9 Hz, 1H), 6.61 (s, 1H), 4.38 (t, J = 7. 1Hz, 3H), 3.66 (t, J = 7.1Hz, 3H), 3.28 (q, J = 8.0Hz, 9H), 1.25 (t, J = 8.0Hz, 13H). 13 C NMR (101MHz, DMSO-d6) δppm: 162.08, 153.85, 151.08, 150.59, 146.64, 143.38, 140.68, 129.68, 128.05, 122. 90,119.88,117.08,116.15,111.58,101.85,67.36,66.20,54.53,53.55,9.32.MS(MALDI-TOF):calculated for C 47 H 63 BBr5F2N5O3S4[M-3Br+H],1082.2191; found,1083.2181.

[0198] [Example 17]

[0199] Photodynamic assay for the proliferation of human esophageal cancer Eca-109 cells

[0200] Test cells: human esophageal cancer cells Eca-109.

[0201] Light source: XD-650AB laser; SD2490 laser power meter.

[0202] Test drugs: 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(N,N,N-triethyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indonetetraene (I1); 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(N,N-diethyl-N-methyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indonetetraene (I2); 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(pyridyl)ethyl)carbamoyl)phenyl]-4 -Boron-3a,4a-diaza-s-indonetetraene (I3); 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(quinolinyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indonetetraene (I4); 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(triphenylphosphonium)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indonetetraene (I5); 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[4-(2-(N,N,N-triethyl)ethoxy) [Phenyl]-4-boron-3a,4a-diaza-s-indanotrane (I6); 2,3; 5,6-di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,5-di(2-(N,N,N-triethyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indanotrane (II1); 2,3; 5,6-di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,5-di(2-(N,N-diethyl-N-methyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indanotrane (II2); 2,3; 5,6-di[thiophene[3,2-b]thiophene]-4,4 -Difluoro-8-[3,5-bis(2-(N,N,N-triethyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indonetetraene (II6); 2,3; 5,6-bis[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-bis(2-(N,N-diethyl-N-methyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indonetetraene (II7); 2,3; 5,6-bis[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,5-bis(2-(N,N,N-triethyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indonetetraene (II6) 16); 2,3; 5,6-Di[2-bromothiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,5-di(2-(N,N-diethyl-N-methyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II 17 ); 2,3; 5,6-Di[2-(2-bromo-thienyl)-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-di(2-(N,N,N-triethyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II 26 ); 2,3; 5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,4,5-tris(2-(N,N,N-triethyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II 36 ); 2,3; 5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,4,5-tris(2-(pyridyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II 38 ); 2,3; 5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,4,5-tris(2-(N,N-diethyl-N-methyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II 47 ).

[0203] Comparison drug: Temopofen.

[0204] Photodynamic antitumor cell proliferation experiment:

[0205] Eca-109 cells in the logarithmic growth phase were collected by centrifugation at 5 × 10⁻⁶. 4 The culture medium was seeded at a density of 1 / mL in 96-well plates and incubated overnight to allow adhesion. The next day, the old culture medium was removed, the compound was added, and incubation continued for 24 hours. Then, a 650nm laser (power density 18mW / cm²) was used. 2 The light dose was 6 J / cm. 2 The culture was subjected to light treatment. Four hours before the end of the culture period, 20 μL of 5 mg / mL MTT solution was added to each well, followed by 150 μL of DMSO. The absorbance at 570 nm was measured using a microplate reader. The experiment was repeated three times. The results are shown in Table 1. The results revealed that compound I... 1-4 I6, II 1-2 II 6-7 II 16-17 II 26 II 36 II 38 II 47It exhibits significant photodynamic antitumor activity against human esophageal cancer cells, all of which are superior to the control drug temopofen. Among them, compound II7 has the most significant photodynamic antitumor activity, with an inhibition rate as high as 97.54%.

[0206] Table 1. Inhibitory effects of compounds on the proliferation of human esophageal cancer cells Eca-109.

[0207]

[0208] Compared with the control drug temopofen, * P<0.05, ** P<0.01, *** P<0.001.

[0209] [Example 18]

[0210] Photodynamic in vitro antibacterial activity against Gram-positive and Gram-negative bacteria

[0211] Test strain: Gram-positive bacteria: Staphylococcus aureus

[0212] Gram-negative bacteria: Escherichia coli

[0213] Light source: XD-650AB laser; SD2490 laser power meter.

[0214] Test drugs: 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(N,N,N-triethyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indonetetraene (I1); 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(N,N-diethyl-N-methyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indonetetraene (I2); 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(pyridyl)ethyl)carbamoyl)phenyl]-4 -Boron-3a,4a-diaza-s-indonetetraene (I3); 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(quinolinyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indonetetraene (I4); 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(4-(2-(triphenylphosphonium)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indonetetraene (I5); 2,3;5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[4-(2-(N,N,N-triethyl)ethoxy) [Phenyl]-4-boron-3a,4a-diaza-s-indanotrane (I6); 2,3; 5,6-di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,5-di(2-(N,N,N-triethyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indanotrane (II1); 2,3; 5,6-di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,5-di(2-(N,N-diethyl-N-methyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indanotrane (II2); 2,3; 5,6-di[thiophene[3,2-b]thiophene]-4,4 -Difluoro-8-[3,5-bis(2-(N,N,N-triethyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indonetetraene (II6); 2,3; 5,6-bis[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-bis(2-(N,N-diethyl-N-methyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indonetetraene (II7); 2,3; 5,6-bis[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,5-bis(2-(N,N,N-triethyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indonetetraene (II6) 16); 2,3; 5,6-Di[2-bromothiophene[3,2-b]thiophene]-4,4-difluoro-8-[(3,5-di(2-(N,N-diethyl-N-methyl)ethyl)carbamoyl)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II 17 ); 2,3; 5,6-Di[2-(2-bromo-thienyl)-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,5-di(2-(N,N,N-triethyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II 26 ); 2,3; 5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,4,5-tris(2-(N,N,N-triethyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II 36 ); 2,3; 5,6-Di[thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,4,5-tris(2-(pyridyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II 38 ); 2,3; 5,6-Di[2-bromo-thiophene[3,2-b]thiophene]-4,4-difluoro-8-[3,4,5-tris(2-(N,N-diethyl-N-methyl)ethoxy)phenyl]-4-boron-3a,4a-diaza-s-indenpaterene (II 47 ).

[0215] Control drug: Methylene blue (MB).

[0216] Photodynamic antibacterial proliferation experiment:

[0217] Staphylococcus aureus and Escherichia coli stored at -80℃ were inoculated into 10 mL of LB broth and cultured overnight at 37℃ with a shaker at 120 rpm. A loopful of bacterial culture was then inoculated into agar medium using the streak plating method (one loop per four zones) and incubated overnight at 37℃. Single colonies were then picked and inoculated into 20 mL of LB broth and cultured for 7 hours at 37℃ with a shaker at 120 rpm. The bacterial concentration was adjusted to 2 × 10⁻⁶ using LB broth. 6 CFU / mL was mixed with drug diluent at a 1:1 volume ratio and added to 24-well plates, ensuring the process is protected from light. The 24-well plates were then incubated at 37°C on a shaker at 120 rpm for 30 min, followed by irradiation with a 650 nm laser (light dose of 20 J / cm²). 2 The optical power density is 440 mW / cm². 2 After that, dilute the bacterial solution with distilled water by 10%. 4After mixing thoroughly, take 1 mL of each solution and spread it evenly on a plate using a spreader. Let stand for 10 minutes, then invert the plates and incubate overnight at 37°C. Use a colony counter to photograph and record the bacterial count. The experimental results show that I1 and I... 3-6 II 1-2 II 6-7 II 16-17 II 26 II 36 II 38 II 47 It exhibits significant photodynamic inhibition against both Gram-positive bacteria (Staphylococcus aureus) and Gram-negative bacteria (Escherichia coli), with compound II7 showing the most pronounced photodynamic antibacterial effect.

[0218] Table 2. Photodynamic antibody activity of new compounds against bacterial proliferation

[0219]

[0220] Staphylococcus aureus group: Compared with the control drug methylene blue, a P<0.05, aa P<0.01, aaa P<0.001.

[0221] Escherichia coli group: Compared with the control drug methylene blue, b P<0.05, bb P<0.01, bbb P<0.001.

Claims

1. A novel class of cationic fused-ring conjugated pyrrole derivatives, characterized by: It has the following structures (I) and (II): where A is -(CH2) m -,-(CH2) m C(CH3)2-,-(CH2) m CH(CH3)-,-(CH2) m O(CH2) n -,-(CH2) m S(CH2) n -,-(CH2) m O(CH2) m C(CH3)2-,-(CH2) m O(CH2) m CH(CH3)-,-(CH2) m S(CH2) m C(CH3)2-,-(CH2) m S(CH2) m CH(CH3)-,-(CH2) m (OCH2CH2) p -,-(CH2) m CO(CH2) m C(CH3)2-,-(CH2) m CO(CH2) m CH(CH3)-,-(CH2) m CONH(CH2) n -,-(CH2) m CONH(CH2) n C(CH3)2-,-(CH2) m CONH(CH2) n CH(CH3)-,-R 5 (CH2) m C(CH3)2-,-R 5 (CH2) m CH(CH3)-,-R 5 O(CH2) n -,-R 5 O(CH2) m C(CH3)2-,-R 5 O(CH2) m CH(CH3)-,-R 5 (OCH2CH2) p -,-R 5 CO(CH2) m CH(CH3)-,-R 5 CO(CH2) m C(CH3)2-, m = 0 - 7, n = 1 - 7, p = 1 - 5; where R 5 is -CH[(CH2) m CH3], -CH[(CH2) n OCH3], -CH[(CH2) n OH], -CH[(CH2) m COOH], -CH[(CH2) m O(CH2) n C(CH3)3], -CH[(CH2) m COO(CH2) m CH3], -CH[(CH2) m (OCH2CH2) n CH3)], -CH[(CH2) m CO(CH2) n C(CH3)3], -CH[(CH2) m CO(CH2) n CH(CH3)2], -CH[(CH2) m CONH(CH2) n C(CH3)3] - CH((CH2) m CONH[CH2) n CH(CH3)2], m = 0 - 7, n = 1 - 7; Where Y = Cl,Br,I; X is H, Cl, Br, I. Where Z = O, S, Se; R 2 ,R 3 ,R 4 =-H,-F,-Cl,-Br,-I,-OH,-O(CH2) m CH3,-(CH2) m CH3,-(CH2) m O(CH2) n C(CH3)3,-(CH2) m O(CH2) n CH(CH3)2,-(CH2) m COOH,-(CH2) m CH(CH3)COOH,-(CH2) m C(CH3)2COOH,-(CH2) m OH,-(CH2) m C6H4OH,-(CH2) m CO(CH2) n OH,-(CH2) m O(CH2) n OH,-(CH2) m (OCH2CH2) p OH,-(CH2) m R 1 ,-(CH2) m C(CH3)2R 1 ,-(CH2) m CH(CH3)R 1 ,-(CH2) m O(CH2) n R 1 ,-(CH2) m S(CH2) n R 1 ,-(CH2) m O(CH2) m C(CH3)2R 1 ,-(CH2) m O(CH2) m CH(CH3)R 1 ,-(CH2) m S(CH2) m C(CH3)2R 1 ,-(CH2) m S(CH2) m CH(CH3)R 1 ,-(CH2) m (OCH2CH2) p R 1 ,-(CH2) m CO(CH2) m C(CH3)2R 1 ,-(CH2) m CO(CH2) m CH(CH3)R 1 ,-(CH2) m CONH(CH2) n R 1 ,-(CH2) m CONH(CH2) n C(CH3)2R 1 ,-(CH2) m CONH(CH2) n CH(CH3)R 1 Or amino acid derivatives, wherein the amino acid derivatives are: -(CH2) m CONH(CH2) n COOH,-(CH2) m CONHCH(CH3)COOH,-(CH2) m CONH(CH2) n CO(CH2) p COOH,-(CH2) m CONHCH[CH(CH3)2]COOH,-(CH2) m CONHCH[CH2CH(CH3)2]COOH,-(CH2) m CONHCH[CH(CH3)CH2CH3]COOH,-(CH2) m CONHCH(CH2C6H5)COOH,-(CH2) m CON[(CH2) n COOH]2,-(CH2) m CONHCH(COOH)CH2COOH,m=0-7,n=1-7,p=1-5。 2. A class of novel cationic fused-ring conjugated pyrrole derivatives (I) and (II), selected from the following compounds:

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