Molecular tetrahedron nanocage, its preparation, and uses thereof

A process for preparation of a nanocage of Formula (I):

• wherein each A is independently selected and has the formula
• is the point of attachment of A to R;
• each R is independently selected and has the formula
• indicates the point of attachment of R to A;
• R1, R2, and R3 are each independently selected from the group consisting of H, halogen, OH, C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, perfluorinated C1-20 alkyl, aryl, hereroaryl, heterocyclyl, —OC1-20 alkyl, —OC2-20 alkenyl, —OC2-20 alkynyl, —O-perfluorinated C1-20 alkyl, —Oaryl, —COOC1-20 alkyl, —COO perfluorinated C1-20 alkyl, —COOaryl, —CONHC1-20 alkyl, —CONHC2-20 alkenyl, —CONHC2-20 alkynyl, —CONH perfluorinated C1-20 alkyl, —CONH-aryl, —CONH-heteroaryl, and —CONH-heterocyclyl, wherein each C1-20 alkyl, C2-20 alkenyl, alkenyl, —OC2-20 alkynyl, —O-perfluorinated C1-20 alkyl, —Oaryl, —COOC1-20 alkyl, —COO perfluorinated C1-20 alkyl, —COOaryl, —CONHC1-20 alkyl, —CONHC2-20 alkenyl, —CONHC2-20 alkynyl, —CONH perfluorinated C1-20 alkyl, —CONH-aryl, —CONH-heteroaryl, and —CONH-heterocyclyl can be optionally substituted from 1 to 3 times with a substituent selected from the group consisting of H, halogen, OH, C1-6 alkyl, aryl, and arylalkyl;
• R4, R4′, and R4″ are each independently selected from the group consisting of H, halogen, C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, perfluorinated C1-20 alkyl, aryl, hereroaryl, heterocyclyl, OH, —OC1-20 alkyl, —OC2-20 alkenyl, —OC2-20 alkynyl, —O-perfluorinated C1-20 alkyl, —Oaryl, —COOC1-20 alkyl, —COO perfluorinated C1-20 alkyl, —COOaryl, —CONHC1-20 alkyl, —CONHC2-20 alkenyl, —CONHC2-20 alkynyl, —CONH perfluorinated C1-20 alkyl, —CONH-aryl, —CONH-heteroaryl, and —CONH-heterocyclyl, wherein each C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, perfluorinated C1-20 alkyl, aryl, hereroaryl, heterocyclyl, —OC1-20 alkyl, —OC2-20 alkenyl, —OC2-20 alkynyl, —O-perfluorinated C1-20 alkyl, —Oaryl, —COOC1-20 alkyl, —COO perfluorinated C1-20 alkyl, —COOaryl, —CONHC1-20 alkyl, —CONHC2-20 alkenyl, —CONHC2-20 alkynyl, —CONH perfluorinated C1-20 alkyl, —CONH-aryl, —CONH-heteroaryl, and —CONH-heterocyclyl can be optionally substituted from 1 to 3 times with a substituent selected from the group consisting of H, halogen, OH, C1-6 alkyl, aryl, and arylalkyl;
• R5, R5′, and R5″ are each independently selected from the group consisting of H, halogen, OH, —O(CH2)n—(OCH2CH2)m—OC1-6 alkyl, aryl, hereroaryl, heterocyclyl, —OC2-20 alkyl, —O-perfluorinated C1-20 alkyl, —Oaryl, and —NR10R11;
• R6, R7, R8, and R9 are each independently selected at each occurrence from the group consisting of H, halogen, C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, perfluorinated C1-20 alkyl, aryl, hereroaryl, heterocyclyl, OH, —OC1-20 alkyl, —OC2-20 alkenyl, —O-perfluorinated C1-20 alkyl, —OC2-20 alkynyl, aryl, heteroaryl, heterocyclyl, and —COOC1-20 alkyl, —COO perfluorinated C1-20 alkyl, —COOaryl, —CONHC1-20 alkyl, —CONHC2-20 alkenyl, —CONHC2-20 alkynyl, —CONH perfluorinated C1-20 alkyl, —CONH-aryl, —CONH-heteroaryl, and —CONH-heterocyclyl, wherein each C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, perfluorinated C1-20 alkyl, aryl, hereroaryl, heterocyclyl, —OC1-20 alkyl, —OC2-20 alkenyl, —OC2-20 alkynyl, —O-perfluorinated C1-20 alkyl, —Oaryl, —COOC1-20 alkyl, —COO perfluorinated C1-20 alkyl, —COOaryl, —CONHC1-20 alkyl, —CONHC2-20 alkenyl, —CONHC2-20 alkynyl, —CONH perfluorinated C1-20 alkyl, —CONH-aryl, —CONH-heteroaryl, and —CONH-heterocyclyl can be optionally substituted from 1 to 3 times with a substituent selected from the group consisting of H, halogen, OH, C1-6 alkyl, aryl, and arylalkyl;
• R10 and R11 are each independently selected from the group consisting of H, C1-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, aryl, heteroarylalkyl, heterocyclylalkyl, and arylalkyl, wherein each C1-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, aryl, heteroarylalkyl, heterocyclylalkyl, and arylalkyl can be optionally substituted from 1 to 3 times with a substituent selected from the group consisting of H, C1-6 alkyl, heteroarylalkyl, heterocyclylalkyl, and arylalkyl;
• X1 and X2 are absent or are independently selected from the group consisting of C1-6 alkylene, C3-8 cycloalkylene, and arylene, wherein C1-6 alkylene, C3-8 cycloalkylene, and arylene can be optionally substituted from 1 to 3 times with H or C1-6 alkyl;
• p is 1 to 3;
• n is 1 to 10;
• and
• m is 1 to 10, said process comprising:
• providing one or more compounds of Formula (II) having the structure:
• and
• forming the nanocage of Formula (I) from the one or more compounds of Formula (II).

A method for detecting an analyte in a fluid comprising:

• providing a sensor comprising a nanocage of Formula (I):
• wherein each A is independently selected and has the formula
• is the point of attachment of A to R;
• each R is independently selected and has the formula
• indicates the point of attachment of R to A;
• R1, R2, and R3 are each independently selected from the group consisting of H, halogen, OH, C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, perfluorinated C1-20 alkyl, aryl, hereroaryl, heterocyclyl, —OC1-20 alkyl, —OC2-20 alkenyl, —OC2-20 alkynyl, —O-perfluorinated C1-20 alkyl, —Oaryl, —COOC1-20 alkyl, —COO perfluorinated C1-20 alkyl, —COOaryl, —CONHC1-20 alkyl, —CONHC2-20 alkenyl, —CONHC2-20 alkynyl, —CONH perfluorinated C1-20 alkyl, —CONH-aryl, —CONH-heteroaryl, and —CONH-heterocyclyl, wherein each C1-20 alkyl, C2-20 alkenyl, alkenyl, —OC2-20 alkynyl, —O-perfluorinated C1-20 alkyl, —Oaryl, —COOC1-20 alkyl, —COO perfluorinated C1-20 alkyl, —COOaryl, —CONHC1-20 alkyl, —CONHC2-20 alkenyl, —CONHC2-20 alkynyl, —CONH perfluorinated C1-20 alkyl, —CONH-aryl, —CONH-heteroaryl, and —CONH-heterocyclyl can be optionally substituted from 1 to 3 times with a substituent selected from the group consisting of H, halogen, OH, C1-6 alkyl, aryl, and arylalkyl;
• R4, R4′, and R4″ are each independently selected from the group consisting of H, halogen, C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, perfluorinated C1-20 alkyl, aryl, hereroaryl, heterocyclyl, OH, —OC1-20 alkyl, —OC2-20 alkenyl, —OC2-20 alkynyl, —O-perfluorinated C1-20 alkyl, —Oaryl, —COOC1-20 alkyl, —COO perfluorinated C1-20 alkyl, —COOaryl, —CONHC1-20 alkyl, —CONHC2-20 alkenyl, —CONHC2-20 alkynyl, —CONH perfluorinated C1-20 alkyl, —CONH-aryl, —CONH-heteroaryl, and —CONH-heterocyclyl, wherein each C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, perfluorinated C1-20 alkyl, aryl, hereroaryl, heterocyclyl, —OC1-20 alkyl, —OC2-20 alkenyl, —OC2-20 alkynyl, —O-perfluorinated C1-20 alkyl, —Oaryl, —COOC1-20 alkyl, —COO perfluorinated C1-20 alkyl, —COOaryl, —CONHC1-20 alkyl, —CONHC2-20 alkenyl, —CONHC2-20 alkynyl, —CONH perfluorinated C1-20 alkyl, —CONH-aryl, —CONH-heteroaryl, and —CONH-heterocyclyl can be optionally substituted from 1 to 3 times with a substituent selected from the group consisting of H, halogen, OH, C1-6 alkyl, aryl, and arylalkyl;
• R5, R5′, and R5″ are each independently selected from the group consisting of H, halogen, OH, —O(CH2)n—(OCH2CH2)m—OC1-6 alkyl, aryl, hereroaryl, heterocyclyl, —OC1-20 alkyl, —O-perfluorinated C1-20 alkyl, —Oaryl, and —NR10R11;
• R6, R7, R8, and R9 are each independently selected at each occurrence from the group consisting of H, halogen, C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, perfluorinated C1-20 alkyl, aryl, hereroaryl, heterocyclyl, OH, —OC1-20 alkyl, —OC2-20 alkenyl, —O-perfluorinated C1-20 alkyl, —OC2-20 alkynyl, aryl, heteroaryl, heterocyclyl, and —COOC1-20 alkyl, —COO perfluorinated C1-20 alkyl, —COOaryl, —CONHC1-20 alkyl, —CONHC2-20 alkenyl, —CONHC2-20 alkynyl, —CONH perfluorinated C1-20 alkyl, —CONH-aryl, —CONH-heteroaryl, and —CONH-heterocyclyl, wherein each C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, perfluorinated C1-20 alkyl, aryl, hereroaryl, heterocyclyl, —OC1-20 alkyl, —OC2-20 alkenyl, —OC2-20 alkynyl, —O-perfluorinated C1-20 alkyl, —Oaryl, —COOC1-20 alkyl, —COO perfluorinated C1-20 alkyl, —COOaryl, —CONHC1-20 alkyl, —CONHC2-20 alkenyl, —CONHC2-20 alkynyl, —CONH perfluorinated C1-20 alkyl, —CONH-aryl, —CONH-heteroaryl, and —CONH-heterocyclyl can be optionally substituted from 1 to 3 times with a substituent selected from the group consisting of H, halogen, OH, C1-6 alkyl, aryl, and arylalkyl;
• R10 and R11 are each independently selected from the group consisting of H, C1-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, aryl, heteroarylalkyl, heterocyclylalkyl, and arylalkyl, wherein each C1-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, aryl, heteroarylalkyl, heterocyclylalkyl, and arylalkyl can be optionally substituted from 1 to 3 times with a substituent selected from the group consisting of H, C1-6 alkyl, heteroarylalkyl, heterocyclylalkyl, and arylalkyl;
• X1 and X2 are absent or are independently selected from the group consisting of C1-6 alkylene, C3-8 cycloalkylene, and arylene, wherein C1-6 alkylene, C3-8 cycloalkylene, and arylene can be optionally substituted from 1 to 3 times with H or C1-6 alkyl;
• p is 1 to 3;
• n is 1 to 10;
• and
• m is 1 to 10;
• providing a fluid containing an analyte;
• and
• contacting a fluid containing the analyte with the sensor to capture the analyte in the nanocage and detect the analyte in the fluid.