97475 - Advanced Organic Synthesis for Functional Materials

Learning outcomes

At the end of the course the student has acquired the theoretical basis necessary to design and undertake the synthesis of principal molecular building blocks used in optoelectronics, the covalent fucntionalization of carbon nanoforms, sustainable C-H activation protocols, visible-light photo- and carbocatalysis.

Course contents

Prerequisites: A solid knowledge of basic organic chemistry is required, particularly regarding the synthesis and reactivity of common organic functional groups, with specific focus on the chemical manipulation of π-systems such as alkenes, alkynes, and aromatic compounds. A background in the coordination chemistry of the most common transition metals is also expected.

It is strongly recommended that students have successfully passed the exam "Organic Chemistry of Molecular Materials and Laboratory" before undertaking this course.

Course contents:

1. Main organic components of an OLED device

1.1. Single-layer OLED configuration
1.2. Multiple-layer OLED configuration
1.3. Electron-transporting molecular organic materials and their synthesis
1.4. Hole-transporting molecular organic materials and their synthesis
1.5. Electronic transitions in transition metal complexes
1.6. Tuning towards red light emission
1.7. Tuning towards blue light emission (pyrazolic and benzoimidazolic ligands)

2. Coordination Ir and Pt complexes that exhibit fluorescence at room temperature

2.1 Ir(III) complexes
2.1.1 Synthesis of homoleptic Ir(III) complexes
2.1.2 Fac/mer isomers on octahedrial complexes
2.1.3 Synthesis of heteroleptic complexes
2.1.4 Properties and applications of heteroleptic complexes
2.1.5 Blue-light emmiting Ir(III) complexes
2.1.6 Fluoro-substituted phenylpyridinic ligands
2.1.7 Methods for obtaining “Sky-blu” emmitions
2.1.8. Carbenic ligands

2.1.9 Synthesis of pyridylpyrazolic ligands

2.2 Pt(II) complexes
2.2.1 Synthesis of homoleptic complexes
2.2.2 Synthesis of heteroleptic complexes

 

 

3. WOLED coordination complexes

3.1 Requirements for home lighting
3.2 Performance descriptors of lighting systems
3.3 Types of organic/organometallic systems with white-light emissions
3.4 Two-component multiple-layer WOLED
3.5 Three-component multiple-layer WOLED
3.6 Two-component single-layer WOLED
3.7 Three-component single-layer WOLED
3.8 Single polymeric component WOLED

4. Metal catalyzed C-H bond activation

4.1. Definitions of the aliphatic and arylic C-H bond activation reaction
4.2. Mechanisms of the C-H bond activation reactions (Aromatic electrophilic substitution or oxidative insertion)
4.3. Mercuration and stannylation reactions of aromatic compounds
4.4 Ir-catalyzed borylation of aromatic compounds
4.5 Transition metal catalyzed silylation of aromatic compounds
4.6 Ruthenium catalyzed C-C bond formation reactions
4.7 Gold-catalyzed alkene and alkyne hydroarylation reactions
4.8 Palladium-catalyzed alkene and alkyne hydroarylation reactions
4.9 Cross-coupling reactions through C-H bond activation reactions

5. Covalent functionalization of carbon nano-materials

5.1 Chemistry of fullerene and analogoues

5.2 Chemistry of graphene and analogues
5.3 Carbocatalysis

 

6. Redox photocatalysis in organic synthesis

6.1 Basic principles of the photoredox-visible catalysis
6.2 Asymmetric photoredox catalysis
6.3 Chiral cyclometallated Ir(III) complexes: synthesis and applciation in photocatalysis

 

7. Electrosynthesis

6.1 Basic principles of the eChem in organic synthesis
6.2 Applications on reductive processes
6.3 Application on oxidative processes

8. Carbon dioxide as C1-bluilding block in organic synthesis

8.1 Basic concepts in CO2 reactivity
8.2 Carboxylation reactions based on CO2
8.3 Carbonylation reactions based on CO2

 

9. Laboratory practice

9.1 Visible-light assisted organic transformation
9.2 Electrosynthetic organic transformation

Teaching methods

• Lessons will be carried out exclusively in presence; (36 h)

• All classes will per carried out in English;

• Lab classes (8 hours) will be arrange;

• Attdenace to classes is strongly recommended but not compulsory;

 

As concerns the teaching methods of this course unit, all students must attend Module 1, 2 [https://www.unibo.it/en/services-and-opportunities/health-and-assistance/health-and-safety/online-course-on-health-and-safety-in-study-and-internship-areas] online, while Module 3 on health and safety is to be attended in class or on Microsoft Teams according to the modality chosen by the teacher. Information about Module 3 attendance schedule is available on the website of your degree programme.

Assessment methods

The exam is oral and requires the prior submission of a short written report related to the laboratory activity.

Oral exam procedure: The oral exam, lasting approximately 30 minutes, includes a PowerPoint presentation (about 10 minutes) by the student on a topic/article of their choice, focused on one of the subjects covered in the course. This is followed by a Q&A session, with questions ranging from topics related to the presentation to others covered during the lectures. The student’s performance in the oral exam is graded on a scale of 26/26 points.

Assessment criteria for the laboratory and scientific report: At the end of the course, each student is assigned a literature article related to either a photocatalytic or electrosynthetic methodology that is closely connected to the reaction performed in the laboratory. At least 10 days before the oral exam, the student must submit a brief written report (about 4 pages) addressing the following key points: a short description of the transformation presented in the article, highlighting its synthetic or mechanistic significance, novelty, strengths, and any weaknesses. The report should also emphasize similarities and differences between the transformation in the article and the one carried out in the lab.

The student’s performance in the lab and the written report is evaluated on a scale of 7/7 points, divided as follows: 3 points are assigned at the end of the laboratory sessions based on the student’s conduct and performance, as evaluated by the course instructor. This evaluation will be communicated anonymously and collectively. 4 points are awarded based on the quality of the written scientific report.

The overall grade is the sum of the points obtained in the oral exam and the laboratory evaluation.

An overall grade of "not sufficient" (score < 18/30) indicates significant gaps in course content, failure to answer questions, or inadequate responses. The scores from the laboratory practice and the report are never insufficient by themselves.

An overall grade of "sufficient to fair" (18–24/30) indicates an acceptable level of preparation, but with noticeable gaps in knowledge or inadequately studied topics.

An overall grade of "good" (25–28/30) indicates that the student has a solid understanding of the course content and is able to make connections between different parts of the program. The student also successfully addressed the laboratory component and submitted a well-constructed report.

An overall grade of "excellent" (29–30/30 cum laude) indicates a thorough and in-depth preparation across the entire course program, with a clear and coherent understanding. The laboratory report is also of high quality and demonstrates extensive knowledge of the experimental techniques discussed during the practical sessions.

 

Students with learning disorders and\or temporary or permanent disabilities: please, contact the office responsible (https://site.unibo.it/studenti-con-disabilita-e-dsa/en/for-students ) as soon as possible so that they can propose acceptable adjustments. The request for adaptation must be submitted in advance (15 days before the exam date) to the lecturer, who will assess the appropriateness of the adjustments, taking into account the teaching objectives.

Teaching tools

Slides will be provided to the students. No comprehensive monographs dealing with all the topics of the course are available in the market.

Course organization: 40 hours theoretical teaching - 8 hours pratical courses.

Office hours

See the website of Marco Bandini